Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration

(54) Title: PROCESS FOR THE MANUFACTURE OF A POLYESTER POLYMER, POLYESTER POLYMER COMPOSITION, AND, BOTTLE PREFORM (30) Unionist Priority: 02/02/2007 us 11/701794 (73) Holder (s) : Eastman Chemical Company (72) Inventor (s): Mary Therese Jernigan (74) Attorney (s): Momsen, Leonardos & CIA.

(86) International Order: pct US2008000560 of 16/01/2008 (87) International Publication: wo 2008 / 0974i7de 14/08/2008 (57) Summary: process for the manufacture of a POLYMER POLYMER, POLYMER POLYMER COMPOSITION, AND, BOTTLE PREFORM. Polyester polymer comprising alkylene arylate units, said polymer having an intrinsic viscosity of 0.72 dl / g, a vinyl terminal concentration of at least 0.8 microequivalent per gram, an AA generation rate less than 20 ppm are prepared by adding a catalyst deactivator or finally in polycondensation or when re-melting a solid polyester polymer.

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Ρ 0806626-4 "PROCESS FOR THE MANUFACTURE OF A POLYESTER POLYMER, POLYESTER POLYMER COMPOSITION, AND, BOTTLE PREFORM"

1. Field of invention

The present invention relates to a polyester polymer, a process for producing a polyester polymer, a solid polyester polymer particle, and a molded product thereof. More particularly, the present invention relates to a polyester polymer comprising alkylene arylate units and said polymer having an intrinsic viscosity of at least 0.72 dl / g, a concentration of vinyl end groups ("VEG") of at least minus 0.8 microequivalents per gram, an acetaldehyde generation rate of less than 20 ppm, and a process for producing such a polyester polymer, a solid particle of such a polyester polymer, and a molded product made from such a polyester polymer.

2. Fundamentals of the Invention

Polyester polymers and especially polyethylene terephthalate polymer are widely used for various applications, such as, sheets, frames, extrusion blow molded bottles, extruded laminates, containers, and beverage bottles. The physical characteristics that make polyester polymers and polyester polymer particles such as ethylene terephthalate (PET) desirable for packaging applications include impact resistance, moldability, clarity, transparency, and little color. However, depending on the specific application, there are other characteristics and properties that are especially desirable for stretch blow molded articles such as CSD and water bottles.

For example, a normally desired characteristic of polyester polymer fusions and solid particles (eg, granules) derived from them is a relatively high molecular weight, generally expressed as inherent viscosity ("lhV") or intrinsic viscosity ("It.V ”). To achieve high values ​​of intrinsic viscosity, a known technique is to employ polymerization in solids (i.e., "solid state treatment"). In general, solid state treatment is a process by which the average molecular weight of the polyester polymer solids is increased. A certain minimum level of crystallization is a prerequisite for treatment in the solid state because otherwise the solid particles would stick together at the temperatures of the treatment of the solid state. During solid state treatment, crystallization continues both in terms of increasing the percentage of crystallinity and increasing the perfection of the crystals, which manifest themselves as an increase in the melting point. For example, partially crystallized PET granules can be subjected to close temperatures, but below crystalline melting temperature for up to 12 hours in a fluidized bed allowing PET granules to increase their intrinsic viscosity while the crystallinity of PET also increases. A flow of inert gas or vacuum can be used to remove compounds that are volatile at temperatures in solid state treatment including the acetaldehyde present in the solid polyester particles. Although it is desirable to eliminate solid state treatment, the absence of solid state treatment makes removal of acetaldehyde problematic. The situation is further complicated by the presence of acetaldehyde precursors that can later generate acetaldehyde when the polyester particles are melted (for example, during injection molding of PET bottle preforms). During solid state treatment, there is some reaction of AA precursors, such as VEG with hydroxyethyl (HEG) terminal groups or water, to release AA, which can be partially swept away by inert gas or vacuum. Without solid state treatment, acetaldehyde precursors can remain at the concentration present after polycondensation of the melting phase. In addition, when solid-state treatment is planned, AA precursors are often present in smaller amounts due to the short residence time in the melting phase.

Another characteristic normally desired is a low concentration of acetaldehyde (“AA”). Acetaldehyde has a noticeable taste and can be highly undesirable in beverage container applications. Two categories of AA are of known interest. The first is the free or residual AA contained in the polyester granules or polyester particles used as raw material in injection molding or extrusion blow molding. A second type of AA is an AA preform or the AA generated when PET granules are melted to make bottle preforms. Precursors of AA in solid polyester particles, chemical compounds or chemical functional groups that can react upon melting the polyester, can produce unacceptable levels of AA in the preforms. In addition, new AA precursors are formed when the polyester polymer is maintained in the molten state, as in the case of an injection molding process to manufacture bottle preforms. When preforms are blown into bottles, unacceptably high levels of AA are those that adversely impact the taste of the beverage contained in these bottles. Relatively tasteless drinks, such as water, are particularly negatively impacted by the taste of AA. Many applications for water bottles require lower levels of the AA preform than applications for carbonated soft drinks (“CSD”). Converters that take polyester particles and manufacture bottle preforms would like to have a resin that could be used to make preforms for both water and CSD applications. This would simplify the process of handling the materials in the converter by allowing a feed to the silo or a type of feed to the silo, a product storage area or a type of product storage area etc ... Most resins sold in the water bottle markets it has a lower intrinsic viscosity than those resins sold in the CDS markets. A dual-use resin could have an intrinsic viscosity high enough for CSD applications and an AA generation rate low enough for water bottle applications.

There are several methods by which the problem of high levels of residual AA in solid polyester particles and / or high rates of AA generation when melting is observed. For example, co-pending order 11 / 229,367, filed on September 16, 2005, describes a process for the production of a polyester polymer, more specifically a process for the production of PET polymers, in which the addition of various types from amine salts of phosphorus-containing acids to titanium-catalyzed melting polyester with a relatively high intrinsic viscosity can produce polyester polymers with low AA generation rates and low residual AA. Alternatively or in addition to other methods, converters can add AA removers to CSD resins to obtain an acceptable AA preform for the water market. AA removers add significant cost to the container and often negatively impact the color of the container or making it more yellow or darker as compared to an analogous container without the addition of AA remover. When certain AA removers are used, the level of black stains present in the solid polyester particles and / or in the molded part can also increase, which results in an undesirable increase in the number of black stains in subsequently molded products.

Another example of a normally desirable characteristic of polyester polymer melts and any subsequent polyester particles produced by solidifying the melt is a low concentration of vinyl terminals. Vinyl terminals as represented by the formula -CO2-CH = CH₂ precursors of AA are known. A commonly accepted mechanism through which AA is generated in fused polyester is the cleavage of the inner chain of a polyester polymer chain to form a vinyl end group and a carboxylic acid end group. The VEG can react with a HEG to form residual or free AA and a new internal ester bond. There is a common perception that a strong concentration of vinyl terminals is therefore undesirable because of the vinyl terminal's ability to react and form AA during subsequent melt processing of the polyester polymer.

In addition, US 5,852,164, indicates that the concentration of olefinic terminal groups or olefin terminals, which is the sum of the vinyl terminals, the vinylidene terminals and the methyl cyclohexane terminals, is preferred because it is less than 25 eq / ton in order to improve the heat stability of the melting of highly modified polyester polymers, which in nearly all examples contain about 33 mole percent of 1,4-cyclohexanedimethanol based on the total diol content of 100 mole percent. In general, it is undesirable, especially in molding processes, that the intrinsic viscosity of the polymer decreases significantly when melting as the properties or parts of the resulting article will be negatively impacted. In addition, it is known that vinyl terminals can also polymerize under extreme conditions into polyvinyl esters that can be eliminated to form poly (enes) that can be responsible for the yellow color of PET.

Because vinyl terminals are known precursors of AA, there is a general tendency to operate polyester polymerization processes in the melt phase at temperatures and production rates that inhibit subsequent generation of AA in downstream melt processing applications. This is especially true when an intrinsic viscosity precursor is manufactured in the melting phase, followed by solid state treatment to obtain a product with an intrinsic viscosity that is acceptable for the given application.

What is not generally appreciated is that what is important for AA generation when fusing is not the fact that the VEG concentration is relatively strong, but because or how the VEG concentration was increased. If the VEG level is relatively strong due to an increased finisher temperature with everything else being equal, then the AA level generated when melting a polyester will increase. If the VEG level is relatively strong due to a decreased reaction rate for converting from VEG to AA with all other things being equal, then few VEG will be converted to AA with the result that the VEG level will increase and the level of AA generated when the polyester melts will decrease.

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It is very easy to influence the reaction rate from VEG to AA, which occurs during melt processing, when polyester is manufactured exclusively in the melt phase. This is because efforts to decrease the reaction rate from VEG to AA after fabrication in the melting phase of the polyester precursor often also have a negative impact on the rate of polycondensation during solid state treatment. On the other hand, it is possible to use a conventional process, including solid state treatment, and impact on the reaction rate from VEG to AA at the beginning of the injection molding process or in an earlier extrusion step, such as composition. This approach would often be more costly and / or problematic than the action taken at the end of a melt line to manufacture a product or final intrinsic viscosity.

A polyester polymer with the properties of a relatively strong concentration of vinyl terminals from higher temperatures and low AA generation rates is attractive from an economic perspective. For example, it would be desirable to operate a PET production process with higher temperatures and higher production rates in this way allowing strong concentrations of vinyl terminals to increase to stronger concentrations than other known PET polymers while maintaining comparable rates of AA generation in subsequent processing applications, such as bottle blow molding. Efforts to decrease the rate of reaction from VEG to AA, which increases the level of VEG, will allow higher temperatures to be used in the manufacture of the melting phase, which also increases the level of VEG, and still achieve lower levels of AA generated during molding as compared to the analogous case at a higher temperature but without efforts to decrease the reaction rate from VEG to AA. Decreasing the reaction rate from VEG to AA where the manufacturing temperature is warmer may result in more AA generated or a higher AA preform than in an analogous case with a colder finisher temperature. It should be noted that in order to obtain very low values ​​of the AA preform, it may be necessary to use low to moderate manufacturing temperatures and low to moderate catalyst concentrations in conjunction with decreasing the reaction rate from VEG to AA.

For this reason, there is a need for a polyester polymer with a high intrinsic viscosity produced completely in the melt phase that avoids the costly step of solid state treatment. In addition, the polyester polymer could be treated towards the end of the complete melting phase manufacturing process so that the reaction rate from VEG to AA would decrease; for this reason, the level of VEG in the solid polyester polymer particles increases although the level of AA generated during melt processing or in the AA preform decreases with respect to the case without any treatment. In one embodiment, the polyester polymer could be produced at higher temperatures and higher production, thus resulting in relatively stronger concentrations of vinyl terminals, yet generating low amounts of AA when re-melting in the absence of AA removers. , regarding the case without any treatment. In another embodiment, the need is especially greater for resins for water bottle applications that normally require low levels in the preform and bottles, and in these cases, manufacturing temperatures could be low to moderate, in conjunction with the treatment to decrease the rate of VEG to AA. It would be even more desirable if the same polyester could be used as a raw material in both, soft drink and water bottle applications.

Summary of the Invention

In one aspect of the invention, a process is provided for the manufacture of a polyester polymer comprising:

a) polycondensing a polyester polymer in the presence of one or more polycondensation catalysts;

b) adding at least one additive compound comprising a catalyst deactivating compound for said polyester polymer after said polyester has reached an intrinsic viscosity of at least 0.45 dl / g; and

c) further increasing the intrinsic viscosity of said polyester polymer to an intrinsic viscosity of at least 0.72 dl / g, thereby producing a polyester polymer with a vinyl terminal concentration of at least 0.8 peq / gram, and a rate AA generation less than 22 ppm.

In another aspect of the invention, a polyester polymer composition comprising polyester polymers comprising alkylene arylate units is provided, said polymer having an intrinsic viscosity of at least 0.72 dl / g, a vinyl terminal concentration of at least 0.8 peq / g, and an AA generation rate of less than 22 ppm, or less than 20 ppm.

In another aspect of the invention, a polyester polymer composition comprising polyester polymers comprising alkylene arylate units is provided, said polymer having an intrinsic viscosity of at least 0.72 dl / g, a vinyl terminal concentration of at least 0.8 peq / g, and an AA preform less than 10 ppm, preferably in a 566.99 g preform, when measured under the following conditions: an extruder drum temperature of 285 ° C and a melting residence time of about 2 minutes.

In another aspect of the invention, finished polyester polymer particles comprising polyester polymers comprising aryl alkylene and phosphorus units are provided in an amount of at least 20 ppm based on the weight of said polymer having an intrinsic viscosity of at least 0.7 dl / g, a vinyl terminal concentration of at least 0.8 peq / g, an AA generation rate of less than 22 ppm, and a crystallinity of at least 10%, wherein the weight of the individual particles is in the range of 0.01 to 10 grams.

In another aspect of the invention, there is provided a molded product obtained by feeding directly or indirectly the finished polyester polymer particles comprising polyester polymers comprising aryl alkylene and phosphorus units in an amount of at least 20 ppm based on the weight of said polymer, said polymer having an intrinsic viscosity of at least 0.7 dl / g, a vinyl terminal concentration of at least 0.8 peq / g, an AA generation rate of less than 22 ppm at a temperature of 295 ° Celsius for 5 minutes, and a crystallinity of at least 10%, where the weight of the individual particles is in the range of 0.01 to 10 grams, for a melt processing zone, melting the particles to form a polyester melt, and forming a molded product from the polyester melt.

4. Detailed Description of the Invention

The present invention can be more readily understood through the following detailed reference of the invention.

It should also be noted that, as used in the specification and appended claims, the singular forms "one", "one" and "a, o," include their referents in the plural unless the context clearly indicates otherwise. For example, a reference to the processing or manufacturing of a “polymer”, a “preform”, an “article”, a “container” or a “bottle” is designed to include the processing or manufacturing of a plurality of polymers, preforms, articles, containers or bottles.

References to a composition containing "an" ingredient or "a" polymer are intended to include other ingredients or other polymers, respectively, in addition to the aforementioned.

The expression of a range includes all integers and fractions thereof within the range. The expression of a temperature or temperature range in a process, or a reaction mixture, or a melt or applied to a melt, or a polymer or applied to a polymer means in all cases that the limitation is satisfied whether or the applied temperature, the actual melting temperature or polymer, or both are at the specified temperature or within the specified range.

The word "composition" means that each ingredient listed is present in the composition, and does not imply that any ingredient in the composition is unbound or unreacted. The composition can be solid or fused. The ingredients specified in the composition can be linked, unbound, reacted, unreacted, and unless otherwise specified, in any oxidation state. The intrinsic viscosity values ​​described throughout this description are specified in units dL / g as calculated from the inherent viscosity measured at 25 ° C in 60% phenol and 40% 1,1,2,2-tetrachlorethane by weight. Polymer samples are dissolved in the solvent at a concentration of 0.25 g / 50 ml. For samples in the Examples section, the viscosity of the polymer solutions is determined using a Rheotek glass capillary viscometer. The description of the operating principle of this viscometer can be found in ASTM 4603. The inherent viscosity is calculated from the measured viscosity of the solution. The following equations describe such measurements of solution viscosity and subsequent calculations for inherent viscosity and from inherent viscosity for intrinsic viscosity:

üinh = [In (t_s/ t₀)] / C where üinh ⁼ Inherent viscosity at 25 ° C with a polymer concentration of 0.5 g / 100 ml of 60% phenol and 1,1,2,2-tetrachlorethane 40% by weight ln = Natural logarithm t_s = Time of sample flow through a capillary tube t₀ = Flow time without solvent through a capillary tube C - Concentration of polymer in grams per 100 ml of solvent (0.50%)

Intrinsic viscosity is the limit value of infinite dilution of the specific viscosity of a polymer. And it is defined by the following equation:

flint = lim (q_sp/ C) = lim (ln q_r) / CC ^ 0 C-&gt; 0 where

T |_int = Intrinsic viscosity η_Γ = Relative viscosity = t_s/1₀T)_sp = Specific viscosity = η_Γ - 1

The calibration of the instrument involves testing in triplicates of a standard reference material and then applying the appropriate mathematical equations to produce the "accepted" intrinsic viscosity values. The three values ​​used for calibration must be within the 0.010 range; if not, correct the problems and repeat the standard test until three consecutive results within this range are obtained.

Calibration Factor = Inherent Viscosity Accepted from Reference Material / Average Determinations of Triplicates

The intrinsic viscosity (It.V. or q_int) can be estimated using the Billmeyer equation as follows:

η_ίηί = 0.5 [and^{0.5 x Ih v}·^corrected -1] + (0.75 x corrected IH.V.)

The reference for estimating intrinsic viscosity (ratio

Billmeyer) is J. Polymer Sci., 4, pgs. 83 - 86 (1949).

Alternatively, the viscosity of the polymer solutions is determined using a modified Viscotek differential viscometer. The description of the operating principle of differential pressure viscometers can be found in ASTM D 5225. The inherent uncorrected viscosity (fin) of each sample is calculated from the Viscotek Model Y501 Ratio Viscometer using the following equation:

il_inh = [ln P₂/ KP,)] / C where

P₂ = The pressure in capillary P₂Pi = Capillary pressure Pi ln = Natural logarithm

K = Constant viscosity obtained from reading a baseline

C = Concentration of polymer in grams per 100 ml of solvent

The corrected inherent viscosity, based on calibration with standard reference materials, is calculated as follows:

Corrected Inherent Viscosity = Calculated Inherent Viscosity x Calibration factor

PET samples containing antimony and / or phosphorus were tested for metals using X-ray fluorescence spectroscopy (XRF), since they were samples containing titanium and / or phosphorus. PET samples containing aluminum, lithium and / or phosphorus were tested for metals using inductively copulated plasma spectroscopy by optical emission induction (ICP-OES). For samples in the Examples section, a wet ash method for ICP-OES involved digesting PET in nitric and sulfuric acid on a hot plate before analyzing an aqueous sample. There is more history of greater possible previous contamination in ICP measurements for aluminum in PET than for lithium in PET. For Example 2, the levels of Al and Li are measured in duplicate on a quartz utensil to minimize previous aluminum contamination. A single test on the standard utensil is reported for the other examples. A procedure follows.

Sample Preparation:

Approximate weight 1.0 g of polymer inside a 100 ml quartz beaker. Add 5 ml of H₂ONLY₄ focused. Cover with a watch glass. Prepare a blank method in the same way except to delete the sample. Place the beakers on the hot plate and heat at low setting (~ 100 ° C) until it starts to singe. At this point start adding HNO₃ concentrated in drops, gradually increasing the heat, until the solution becomes clear. Reflux for approximately 30 minutes with the highest heat setting (approximately 400 ° C). Cool to room temperature. Quantitatively transfer the contents of the beaker into a 100 ml volumetric flask. Add the internal standard Sc with a level of 1 ppm and dilute to the 18 Mohm water mark.

Analysis using spectroscopy of inductively copulated plasma by optical emission induction (ICP-OES).

Instrument Configuration:

Spray chamber: Cyclonic Quartz glass - without bulkheads

<td>Nebulizer:</td><td>Concentric Quartz Glass</td>

<td>Injector:</td><td>Quartz ID 2 mm</td>

<td>Plasma Energy:</td><td>1450 Watts</td>

<td>Plasma Airflow:</td><td>18 1 / min</td>

<td>Aux Flow:</td><td>0.2 1 / min</td>

<td>Neb flow:</td><td>0.65 1 / min</td>

<td>Sample Absorption: Method Parameters: Analytical Lines:</td><td>1.56 ml / min</td>

<td colspan="2">AI-396,153 nm View of the axial plasma</td>

<td colspan="2">Li - 670.784 nm View of the radial plasma Internal Standard Line:</td>

<td colspan="2">Sc - 361.383 nm View of the axial plasma</td>

Calibrate the instrument - 2 calibration points using a 15 blank calibration control and NIST traceable standards prepared at a level of 1 ppm.

Aspirate the samples and analyze using 3 replicates. Report the average of the 3 replicates.

The concentration values ​​of vinyl terminals described 20 through this description are specified in microequivalents per gram (peq / g) or millimoles per kilogram (mmoles / kg). The concentration of vinyl terminals can be measured in solid particles or preforms.

Vinyl terminals are represented by the formula CO2-CH = CH2.

A small amount of polyester sample, typically 25 0.4 grams, is weighed to the nearest mg and placed in a 240 gram screw top flask along with a Teflon coated stir bar. A mixture of fresh solvent (solution A) is prepared with volume ratios measuring 75 parts of chloroform-d (from Aldrich Chemical Company), 19 parts of trifluoroacetic acid, and 6 parts of trifluoroacetic anhydride. 4.00 ml of solution A is added to the sample bottle and the bottle is closed and sealed. The flask is heated to 50 ° C in a metal block and shaken for 16 hours. The vial is then removed from the block and cooled. A fresh solution (solution B) is prepared with exact volume ratios by mixing 2 parts of solution A and one part of acetic acid. The flask is opened and 1 ml of solution B and 50 microliters of a, a, a-trifluorotoluene are added to the flask. The bottle is closed and mixed well. A portion of the prepared solution is loaded into an NMR tube, and an NMR spectrum is recorded for analysis on a Bruker Advance 500 MHz instrument using conditions that provide quantitative signals for the 19 fluorine NMR experiment. The key conditions of the NMR instrument are; Pulse delay - 5 sec .; Scan width - 32,795 ppm; Number of scans measured 512; Number of points -65536; Extension of the 2.0 MHz line. Chemical displacement is recommended at 13.0 ppm with the signal a, a, atrifluorotoluene (TFT). The area of ​​the a, a, a-trifluorotoluene signal including the area of ​​the high rotation bands and carbon side bands 13 is measured exactly together with the exact signal area of ​​the vinyl end group. If the signal from the vinyl end group is not resolved at the baseline from the adjacent peaks, the area can be measured using curve configuration methods or other acceptable methods of area measurement. In the formula below, a correction factor multiplier of 1.1 is used to correct the area of ​​the vinyl end group to improve accuracy. The standard deviation method is 0.43 mmol / kg (peq / g) at the concentration of vinyl terminals of 5.6 mmol / kg (peq / g) and 0.11 mmol / kg (peq / g) at the concentration of terminals vinyls of, 76 mmol / kg (peq / g).

Representative calculations are shown below;

(Peak area of ​​the group having min al vinyl) ,,, _J ...... * 1.1 * 0.0595 * 1.000000 mmol / kg of the groups having maximum mm mm = - {Peak area TFT) * 146.1 {Weight of the sample in g)

The free AA values ​​described through this description are specified in units of ppm. The AA generation rates specified for this invention are specified in units of ppm. To determine the AA generation rates for any granules or articles, the following test method is employed. The granule or article is melted in a plastometer for extrusion at 295 ° C for 5 minutes.

Free AA can be measured on solid particles or preforms. This test method is used to measure the level of free acetaldehyde in particles, powders, preforms, bottles, and any other shape that the polyester composition may have. For the purpose of measuring residual or free acetaldehyde, the sample is tested according to the method described below.

The test procedure for measuring the level of free acetaldehyde in a sample, whether a preform, granule, powder, or otherwise is the ASTM test method # F2013-00. Samples are cryogenically ground using a Wiley mill equipped with a 1.0 mesh screen. The final milled material has a particle size less than 800 pm. A portion of a sample (0.20 g) is weighed in a 20-ml flask with space at the top, sealed and then heated to 150 ° C for sixty minutes. After heating, the gas above the sealed sample of PET polymer is injected into a GC capillary column. The acetaldehyde is separated, and the ppm of acetaldehyde present in the sample is then calculated. The calculated amount of acetaldehyde represents the amount of free or residual acetaldehyde present in the sample.

To measure the rate of acetaldehyde generation in the preforms, it is sufficient to use the ASTM Method # F2013-00 as described above without subjecting the preforms to an additional melt history since due to the manufacture of a preform, the granules are cast in an extruder before injection molding. Through melt extrusion or injection molding, AA precursors in polymer melting have the opportunity to convert to acetaldehyde.

The rate of acetaldehyde generation can be measured in the solid particles. However, for the purpose of measuring the generation of acetaldehyde, the sample must go through a second melting story (where the manufacture of the polyester in the melting phase is told as the first melting story) in order to determine the level of acetaldehyde generated. If the sample is a particle or powder that has not gone through a melting step in addition to a previous manufacturing step in the melting step, the sample is treated first according to the Sample Preparation procedure described below, after which the sample is submitted to the ASTM test method # F2013-00 for analysis.

Sample Preparation: For the purpose of measuring the rate of acetaldehyde generation, and if the sample manufactured exclusively in the melting phase has not undergone a subsequent melting history for the polycondensation of the melting phase, it is prepared according to this method before submitting the sample to the ASTM # F2013-00 test. Samples of polymer powder (ground to pass through a 3 mm screen) are heated in a vacuum oven at 115 ° C (25 - 30 in. Hg) (84.6 - 101.6 kPa) with a 4 SCFH nitrogen purge (0.11 Nm³/ h) for at least 48 hours. Although overnight drying was sufficient to remove water, which is all that is needed for samples treated in the solid state, this extended oven treatment also serves to desorb at about 1 ppm or less the residual AA present in the powder with high IV after synthesis only of the melting phase before the AA generation test. If the granules had not been extracted beforehand from most residual AA (target: 1 ppm or less) it is necessary to desorb the residual AA from the granules. The granules can be milled to pass a 2 mm screen before removing residual AA under the conditions described above. If grinding is not done, it would take much longer and / or would require a higher temperature to desorb the

Residual AA of the granules, to about 1 ppm or less, due to the larger particle size (longer diffusion path). Any suitable acetaldehyde devolatization technique can be employed on the particles which reduces the level of free acetaldehyde to below about 1 ppm or less, including passing hot inert gas over the particles for a period of time sufficient to reduce the residual acetaldehyde to the desired level. Preferably, the acetaldehyde devolatization temperature should not exceed 165 ° C, more preferably, it does not exceed 160 ° C, or even more preferably, it does not exceed 150 ° C. The sample is then placed in a Tinius Olsen extrusion plastometer using a steel rod. The mold orifice is calibrated according to ASTM D 1238. A small amount of material is purged from the bottom, which is then capped. The piston rod assembly is placed on top of the drum. A weight of 225 g can be placed on top of the piston rod to hold the rod underneath the barrel. The polymer is kept at 295 ° C for 5 minutes. The orifice plug is then removed from the bottom of the drum. By means of a heavy weight and pressure from the operator, the extrudate is pushed out of the drum in an ice water bath. The extrudate is beaten dry, sealed in a bag and placed in a refrigerator until the ASTM # F2013-00 test is performed.

Alternatively, a CEAST 7027 Modular Fusion Flow instrument is used. An AA generation program is started that will maintain a temperature of 295 ° C and will extrude the molten PET material in 5 minutes with a constant flow rate as defined by the instrument company. As soon as the extrudate is pushed out of the drum and into a cold water bath, the sample is collected, beaten until dry, sealed in a bag and placed in a refrigerator until the ASTM # F2013-00 test is performed.

Acetaldehyde can be generated in polyester resins with the

Modular Fusion Flow Model CEAST 7027 or any instrument similar to a plastometer for extrusion. However, the Ceast 7027 instrument is preferred because the automated functions of this instrument reduce test variability by maintaining consistent contact times for the polymer within the extrusion drum. This particular instrument model incorporates automated resin packaging at the beginning of the test procedure. The instrument is equipped with a motorized platform that will push the material out of the drum until the plunger is at the specified height above the bottom of the drum. The platform will then hold the piston rod in place, allowing the resin to heat up and generate acetaldehyde. At the end of the specified time, the platform extrudes the rest of the resin out of the barrel while moving at a constant speed. These steps eliminate the possibility of variability in the results of conditioning the material during the final extrusion stage. The variability in polymer loading is reduced with the drum design, but polymer loading is not automated.

Acetaldehyde can be generated in the above manner with a temperature in the range of 265 ° C to 305 ° C. The most consistent results are obtained between 275 ° C and 295 ° C. The duration of time that the resin is kept inside the drum shows good results when between 2 and 15 minutes. The 5 to 10 minute range shows the best repeatability and distinction between materials. For the acetaldehyde generation numbers specified by this invention, 295 ° C and 5 minutes were used.

The use of this method of generation of acetaldehyde and tests allow the screening of polyester resins for generation of acetaldehyde without the need for large quantities of material for evaluations such as molding of bottle preforms. As little as 10 grams of material can be used in this process making it ideal for testing samples in the laboratory.

In the process of the invention, polyester polymers can be manufactured from aromatic or aliphatic dicarboxylic acids, esters of dicarboxylic acids, anhydrides of dicarboxylic acids, acid chlorides of dicarboxylic acids, glycols, epoxides and mixtures thereof. Suitable polyester polymers can be made from diacids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and mixtures thereof, and diols such as ethylene glycol, diethylene glycol, 1,4cyclohexanedimethanol, 1,4-butanediol, 1,3-propanediol, and mixtures thereof.

The process of the present invention can produce polyethylene terephthalate (PET) polyesters, which include "modified" polyesters. Examples of polyester polymers manufactured through the process include polyalkylene terephthalate copolymers and homopolymers modified with one or more modifiers in an amount of 40 moles% or less, less than 15 moles%, or less than 10 moles%. Unless otherwise specified, a polymer includes both its copolymer and homopolymer variants. An example of an especially suitable polyester polymer is a polyalkylene terephthalate polymer, and the preferred ones are polyethylene terephthalate polymers. By "modified" we mean that the diacid component and / or diol component are replaced in part with one or more different diacid and / or diol components.

For example, the diol component such as ethylene glycol in the case of PET can be replaced in part with one or more different diol components, and / or the carboxylic acid component such as terephthalic acid in the case of PET can be replaced in part with a or more components of different carboxylic acids. The molar percentage for all the diacid component (s) totals 100 moles%, and the sum of the molar percentages for all diol components totals 100 moles%.

For example, the carboxylic acid component of the polyester can optionally be replaced with up to 20 mole percent of one or more different carboxylic acids. Such additional carboxylic acids include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or dicarboxylic cycloaliphatic acids preferably having 8 to 12 carbon atoms. Examples of dicarboxylic acids to be included with terephthalic acid include: phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, cyclohexane 1,3-dicarboxylic acid, stylbene acid dicarboxylic acid, cyclohexanodiacetic acid, dodecane-1,2,3-dioic acid, diphenyl-4,4'dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and mixtures thereof. Polyester polymers can be prepared from two or more of the above dicarboxylic acids. In addition, of the preceding carboxylic acids, those that may exist as stereoisomers may be in cis-, trans-, or a mixture thereof.

In addition, for example, the diol component can optionally be replaced up to about 20 mole percent with one more diols other than ethylene glycol. These other diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 3 to 20 carbon atoms. Examples of such diols include: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6- diol, 3-methylpentanediol- (2,4), 2methylpentanediol- (1,4), 2,2,4-trimethylpentanediol- (1,3), 2-ethylhexanediol (1,3), 2,2-diethyl propanediol- (1,3), hexanediol- (1,3), 1,4-di- (hydroxyethoxy) benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy -1,1,3,3tetramethyl-cyclobutane, 2,2-bis- (3-hydroxyethoxyphenyl) -propane, and 2,2-bis- (422 hydroxypropoxyphenyl) -propane, 1,2-cyclohexanediol, 1,4- be prepared from two or more of the above diols. Furthermore, for the preceding diols, those which may exist as stereoisomers may be in eis-, trans-, or mixtures thereof. It should be noted in this regard that the presence of residues of ethylene glycol, OCH₂CH₂O-, is preeminent, as in the absence of such residues, the generation of acetaldehyde does not occur.

The polyester polymers of this invention can optionally contain functional monomers, for example, trifunctional or tetrafunctional comonomers such as, trimethyl anhydride, trimethyl acid, trimethylpropane, pyromelitic dianhydride, pentaerythritol, and the like. However, these are generally not preferred, and when used, they are generally used in much smaller quantities.

The polyester polymers of this invention can optionally contain certain agents that color the polymer. For example, a bluish toner can be added to the melt in order to reduce the b * of the resulting polyester polymer. Such bluing agents include inorganic and organic blue toners. In addition, red toners can also be used to adjust the color to *. Examples of toners include cobalt (II) compounds, such as cobalt (II) carboxylates. Other examples include red and blue toners described in US Pat. Nos.5,372,864 and 5,384,377. The way in which toners are introduced into the polyester polymer is not limited, nor is the amount of toner limited.

The polyester polymers of this invention can optionally contain additives commonly used in polyesters. Such additives include, but are not limited to, dyes, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheating aids, and the like. Still other examples of additives that increase the performance properties of the polyester polymer include crystallization aids, impact modifiers, surface lubricants, detaching agents, antioxidants, UV light absorption agents, colorants, nucleating agents, additives for sticky bottles such as talc and fillers.

The polyester compositions of the invention can be prepared by using polymerization procedures known in the art sufficiently to affect esterification and polycondensation. Processes for making polyester in the melting phase include condensing at least one dicarboxylic acid with at least one diol, optionally in the presence of catalysts for esterification, in an esterification zone, followed by polycondensation in the presence of a polycondensation catalyst in an polymerization zone, which in some cases can be divided into a prepolymer zone and the finishing zone; or ester exchange, often in the presence of a catalyst for transesterification in the ester exchange zone, followed in the presence of a polycondensation catalyst through a polymerization zone and finishing zone. Each of the polymers obtained can optionally be treated in a solid state according to known methods.

To further illustrate, the mixture of one or more dicarboxylic acids, preferably aromatic dicarboxylic acids, or ester forming derivatives thereof, and one or more diols are fed to an esterification reactor or ester exchange reactor operated at a temperature of between about 200 ° C and 300 ° C, typically between 240 ° C and 285 ° C for direct esterification, and at a pressure of between about 1 psig (6.9 kPa) to about 70 psig (482.6 kPa). The residence time of the reagents is typically in the range of about one to five hours. The melting phase reaction proceeds in batch, semi-batch or continuous mode.

Preferably the process of the invention is continuous. Normally, the dicarboxylic acid (s) is / are directly esterified with high pressure diol (s) and at a temperature of about 240 ° C to about 270 ° C. The esterification reaction or ester exchange reaction is continued until an esterification degree of at least 70% is achieved, but more typically until an esterification degree of at least 85% is achieved to manufacture the monomer and / or oligomers desired. The formation of monomer and / or oligomer is not typically catalyzed in the direct esterification process and catalyzed in the ester exchange processes.

Polycondensation catalysts can optionally be added to the esterification zone along with esterification / ester exchange catalysts. If the polycondensation catalyst forms an insoluble salt with the dicarboxylic acid (s) the catalyst can be added after the esterification zone. If a slower production rate results after the polycondensation catalyst has been added to the esterification zone, the catalyst could be added after the esterification zone. If the polycondensation catalyst is added to the esterification zone, it is typically mixed with one or more of the diol components and fed as a mixture to the esterification reactor.

Typical ester exchange catalysts that can be added to the ester or reactor (s) exchange zone, and that can be used separately or in combination include titanium alkoxides, tin (II) or esters (IV), alkali metals or metals alkaline earths such as lithium or calcium, manganese compounds, zinc compounds, magnesium acetates or benzoates, and / or other catalyst materials as are well known to those skilled in the art. In addition, compounds containing phosphorus and some colorants may also be present in the esterification zone. Phosphorus-containing compounds are generally not recommended to be present in an ester exchange zone as ester exchange catalysts can be deactivated prematurely, and more desirably, phosphorus-containing compounds are not added to the esterification zone or to the composition of monomer / oligomer produced in the esterification zone, if the esterification is direct ester exchange esterification.

In the case where the polyester polymer is a PET polymer, the resulting melt of the polyester oligomer formed in the esterification zone and / or ester exchange zone may include bis (2hydroxyethyl) terephthalate (BHET) monomers, low molecular weight oligomers , diethylene glycol DEG, and traces of water quantities as the by-product of the condensation not removed in the esterification zone, along with other traces of impurities from the raw materials and / or possibly formed by catalyzed side reactions, and other optionally added compounds such as toners and stabilizers. The relative amounts of BHET and oligomeric species will vary depending on whether the process is a direct esterification process in which case the amount of oligomeric species is significant and even present as the main species, or an ester exchange process in which case the amount relative to BHET predominates over oligomeric species. The water is removed while the esterification reaction proceeds in order to conduct the balance towards the products. The alcohol produced by the ester raw material is removed as the ester exchange reaction proceeds in order to drive the balance towards the products. In the case of dimethyltereftalate, the alcohol removed is methanol. The esterification zone typically produces the mixture of monomer and oligomer continuously in a series of one or more reactors.

Alternatively, the monomer and oligomer mixture could be produced in one or more batch reactors. It is understood, however, that in a process for the manufacture of polyethylene naphitalate (PEN) polymers, the reaction mixture will contain the monomeric bis (2hydroxyethyl) naphthalate species and their corresponding oligomers, instead of BHET and its corresponding oligomers that will be present when manufacturing PET.

At this stage in the process, intrinsic viscosity is often not measurable or is less than 0.1 dl / g. The average degree of polymerization of the melting of the polyester oligomer is typically less than 15, and can be less than 7.0.

Once the desired degree of stereification is complete, the reaction mixture (that is, the melting of the polyester oligomer) is transported from the esterification reactors in the esterification zone to the polycondensation zone, which may comprise a pre- polymer and a finishing zone. Polycondensation reactions take place in the melting phase in the prepolymerization zone and end in the melting phase in the finishing zone, after which the melting is solidified into a product, or optionally solidified in the form of tablets, granules, or any other model. The solid particles can optionally be crystallized before or after cutting.

The prepolymerization and finishing zones can comprise a series of one or more different reaction vessels operating under different conditions, or the zones can be combined within a reaction vessel using one or more sub-stages operating under different conditions in one single reactor. That is, the prepolymerization zone may involve the use of one or more reactors continuously operated, one or more batch reactors, or even one or more reaction steps or sub-stages carried out in a single reactor vessel. In some reactor designs, the prepolymerization zone represents the first half of the polycondensation in terms of reaction time, while the finishing zone represents the second half of the polycondensation. While other reactor designs can adjust the residence time ratio in the finishing zone to that of the polymerization zone to be about 1.5: 1 or higher, a distinction common in many projects between the prepolymerization zone and the zone finishing process is that the last zone often operates at a higher temperature and / or lower pressure than the operating conditions in the prepolymerization zone. Generally, each of the prepolymerization and finishing zones comprise one or a series of more than one reaction vessel, and the polymerization and finishing reactors are in sequence in a series as part of a continuous process for the manufacture of the polymer polyester.

In the specific case where the fusion of the polyester polymer is a polyalkylene terephthalate or more specifically a polyethylene terephthalate, the prepolymerization zone generally comprises a series of one or more vessels and is operated at a temperature of between about 260 ° C and 300 ° C for a period of about five minutes to four hours, within this zone, the intrinsic viscosity of the oligomer monomers comprising the melting of the polyester polymer at the beginning of the zone is increased to about no more than 0.48 dL / g. As the intrinsic viscosity increases, the diol by-product or by-products are removed from the polyester polymer melt using a vacuum applied in the range of 350 mmHg (46.7 kPa) to 0.2 mmHg (0.03 kPa) in order to to direct the balance towards the products. In this regard, the polyester polymer melt can be subjected to stirring, for example, through a stirring mechanism, to promote the removal of diols from the melt. As the melt is fed into successive vessels, the molecular weight and consequently the intrinsic viscosity of the polymer melt increases. The pressure of each vessel can generally be decreased to promote evaporation of diol allowing for a progressive increase in polymerization in each successive vessel or in each successive zone within the vessel. Alternatively, to promote the removal of glycols, water, alcohols, aldehydes, and other products from the reaction, the reactors can be purged with an inert gas. Inert gas is any gas that does not cause a reaction or undesired product characteristics under the conditions of the reaction. Suitable gases include, but are not limited to, argon, helium and nitrogen.

In the prepolymerization zone, also known in the industry as the low polymerizer, monomers and oligomers with low molecular weight can be polymerized via polycondensation to form a polyester prepolymer of polyethylene terephthalate (or PEN polyester, etc.) in presence of a catalyst. If one or more polycondensation catalysts have not been added in the esterification stage, the polycondensation catalyst can be added in this zone to catalyze the reaction between low molecular weight monomers and oligomers to form a prepolymer and remove the diol as a by-product .

There are numerous polycondensation catalysts known in the art. For example, polycondensation can proceed in the presence of at least one catalytically active metal compound such as titanium, aluminum, antimony, germanium, cobalt, alkali metals, and alkaline earth metals, magnesium, and calcium. In one embodiment, the polyester polymer is devoid of catalytically active compounds of cobalt, germanium, antimony, calcium, activated carbon, and / or magnesium added to the melting process for the manufacture of the polyester polymer.

In one embodiment, a titanium catalyst is provided, preferably in the presence of about 3 ppm (parts per million) to about 35 ppm of titanium in the catalyst, more preferably from 4 to 15 ppm of titanium in the catalyst, and more preferably from 5 to 10 ppm Ti, in each case based on the weight of titanium in the polyester polymer melt.

The titanium catalyst can be any titanium compound that promotes a reasonable rate of polycondensation. Preferably, the catalyst exhibits at least the same rate of polycondensation as that achieved using antimony triacetate or antimony trioxide which are known examples of polycondensation catalysts used in commercial PET manufacture, and more preferably exhibits a considerably higher rate of polycondensation in the absence of deactivating compounds such as phosphoric acid. A catalyst suitable for polycondensation such as a titanium catalyst can be added anywhere in the melting phase process, such as within the esterification zone or in the polycondensation zone. Preferably, the chosen point of addition will not result in a decrease in the rate of polycondensation, which is a decrease in the accumulation of IV, with respect to other possible points of addition. It is preferably added after at least 90% conversion in the esterification zone, or after completing the esterification (which includes ester exchange), or between the esterification zone and the polycondensation zone, or to the beginning of the zone polycondensation, or in the prepolymerization zone, preferably during the first half of the prepolymerization zone, and most preferably during the first quarter of the prepolymerization zone (with respect to the residence time in the zone).

Examples of titanium catalysts suitable for polycondensation generally include titanium (IV) compounds which are alkoxides, glycolates, acetates, oxalates, etc. Mixed glycolate alkoxides and alkoxides are preferred. Titanium (IV) isopropoxide is an example of a preferred catalyst. Many of these catalysts are commercially available, that is, under the trade name of DuPont's Tyzor® titanates. Solid titanium compounds that serve as heterogeneous catalysts are also suitable, including those described in US Patent 5,656,716. Titanium oxides and hydrated oxides can be solubilized during the course of polymerization, for example, by complexing and / or reacting with any diol component. If the catalysts remain insoluble, at least in part, catalytic activity would be a problem, since they would become cloudy (lack of clarity). Soluble catalysts are preferred, more preferably, those catalysts that are soluble at the start of the reaction. The titanium catalyst can be introduced into the reaction in any convenient way. A solution of catalyst in alcohol or a solid liquid mixture (slurry) of catalyst in ethylene glycol can be used, for example, since it can be a solution or slurry of catalyst in an oligomer mixture. The catalyst can also be added alone, and distributed through stirring, for example, through mechanical mixing or through the use of a static mixer.

In another example, an appropriate polycondensation catalyst can be an aluminum compound. Catalytic aluminum compounds can be added to the melt phase process as a compound (which includes a salt or complex) or as a metal providing that it is essentially active as a catalyst in the polycondensation phase or alone or in combination with the compounds or r atoms

alkali metal or alkaline earth metal. Aluminum oxides are not included within the meaning of an aluminum or metal compound. Desirable are aluminum compounds that can be dissolved in a diluent or a vehicle that is volatile and / or reactive with polyester forming ingredients. Suitable reactive liquid vehicles can have any molecular weight, such as those in the range of 62 to about 10,000 grams per mole. Aluminum compounds can also be added as slurries or suspensions in a liquid that is volatile and / or reactive with polyester forming ingredients. Aluminum can also be added to the melt phase process by mixing the aluminum compound with a polyester polymer in a suitable extruder or other device to form a concentrate, and subsequently, preferably melting the concentrate as a melt feed for the process melting phase. A preferred mode of adding aluminum compounds is adding to a catalyst mixing tank, which is part of the polyester melting process equipment. Preferably, the catalyst mixing tank also contains an alkali metal compound or an alkaline earth compound or an alkaline compound as well as an appropriate solvent or dispersing agent.

The aluminum compound can be added to the esterification zone, to the oligomer mixture leaving the esterification zone, or to start polycondensation, or to melt polyester during polycondensation, and preferably as noted above after about 75 % conversion in the esterification zone. An aluminum compound is preferably added when the percentage of conversion of the terminal acid groups in the esterification zone is at least 75%, more preferably when the% of conversion of the terminal acid groups is at least 85%, and more preferably when the % conversion of the terminal acid groups of the esterification is at least 93%. However, since aluminum operates as a polycondensation catalyst, it is desirable to add aluminum to the polyester melt after the monomer / oligomer melt leaves the esterification reactors and is added between the esterification zone and the polycondensation zone, or in the start of or to the prepolymerization zone (the first stage of polycondensation) to provide the benefit of a shorter reaction time or a higher molecular weight accumulation.

In a preferred embodiment, the aluminum compound is added to the oligomer mixture at or after completion of the esterification zone or for a polyester melt no later than when the intrinsic viscosity reaches 0.3 dL / g , or not later than when the intrinsic melt viscosity reaches 0.2 dL / g, and more preferably for the oligomer mixture leaving the esterification zone or before the start or beginning of the polycondensation, which is for or within the prepolymerization zone as the first stage of polycondensation (the finishing zone being the second and last stage of polycondensation).

Aluminum compounds suitable as polycondensation catalysts include aluminum compounds with at least one organic substituent. Illustrative examples of suitable compounds include those of the formula:

Al [OR]_The[OR ']_B[OR ”]_ç[R ”']_d where R, R 'and R ”are independently an alkyl group, an aryl group, acyl group or hydrogen, where preferably at least one of R, R', R” and R '”is not hydrogen, R”' is a anionic group, and a, b, c, d are independently 0 or positive integers, and a + b + c + d is equal to 3 or not greater than 3.

Suitable examples of aluminum compounds include carboxylic acid salts such as aluminum acetate, aluminum benzoate, aluminum lactate, aluminum laurate, aluminum stearate, aluminum alcoholates such as aluminum ethylate, aluminum isopropylate, tri - aluminum butyrate, aluminum tri-tert-butyrate, mono-sec-butoxyaluminium diisopropylate, and aluminum chelates in which the alkoxy group of an aluminum alcoholate is partially or completely replaced by chelating agents such as an alkyl acetoacetate or acetylacetone such as aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), diisopropylate aluminum alkyl acetoacetate, aluminum monoacetylacetate bis (ethyl acetoacetate), aluminum tris (acetylacetate), aluminum acetylacetonate.

Preferred among the aluminum compounds are the basic aluminum carboxylic acid salts and aluminum alcoholates. Basic aluminum carboxylic acid salts include mono-basic and di-basic compounds.

The basic aluminum acetate used can be either the monohydroxy diacetate compound or the dihydroxy monoacetate compound or a mixture thereof. In particular, basic aluminum acetate and aluminum isopropoxide are preferred aluminum compounds. The stabilization of basic aluminum acetate with boric acid can in some cases increase its solubility. Aluminum isopropoxide is more desirable.

A number of aluminum atoms are added to affect polycondensation. Preferred amounts are effective for polycondensation at a reasonable rate. A reasonable fee is one where a polyester line can be operated on and still take over the cost of capital. A more preferred reasonable rate is at least that achieved with 250 ppm Sb. The amount is generally in the range of at least 2 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, or up to about 150 ppm, or up to about 100 ppm, or up to about 75 ppm, or up to about 60 ppm Al based on the weight of the polymer. When used in combination with alkali or alkaline earth metal, a portion of which can be added to the esterification zone, increasing the mole ratio of alkali metal or alkaline earth metal to aluminum (M: A1) can increase the rate of polycondensation; for this reason, low aluminum loads can present a reasonable rate with a moderate to high ratio (M: A1), while presenting slow rates with low M: A1 molar ratios. The preferred rate of aluminum is 3 ppm to 60 ppm, and the most preferred range is 5 to 20 ppm. Other suitable amounts include at least 3 ppm, or at least 5 ppm, or at least 7 ppm, or at least 10 ppm, or up to 60 ppm, or up to 40 ppm, or up to 30 ppm Al, or up to 25 ppm, or up to 20 ppm, or up to 18 ppm, or up to 16 ppm, or up to 15 ppm.

Aluminum compounds can be used in combination with alkali metal or alkaline earth metal. The latter can optionally be present or added to the esterification zone or at any point where the addition of aluminum compounds is made. Alkali metal or alkaline earth metal refers to metals from Group IA and Group IIA of the periodic table, including, but not limited to Li, Na, K, Rb, Cs, Mg, Ca, Sr, and preferably Li, Na or K. Metals can be added to the melting phase as metal compounds (which include a complex or a salt) having counter ions, among which the preferred counter ions are hydroxides, carbonates, and carboxylic acids.

The ratio of moles of alkali metal or moles of alkaline earth metal or moles of alkali to moles of aluminum (M: A1) is generally in the range of at least 0.1, or at least 0.25, or at least 0, 5, or at least 0.75, or at least 1, or at least 2, and up to about 75, up to about 50, up to about 25, up to about 20, up to about 15, up to about 10, or up to about 8, or up to about 6, or up to about 5. To determine the particular amount of aluminum and what M: A1 molar ratio to employ, considerations are taken for the desired reaction rate, which is influenced by the temperature in the polycondensation zone, color, clarity and AA generation rate displayed in the final polymer .

From the prepolymerization zone, once an intrinsic viscosity of no more than 0.48 dL / g is obtained, the polyester polymer melt from the prepolymerization zone is fed to a finishing zone polycondensation where polycondensation is still continued in one or more finishing vessels generally, but not necessarily, elevated to temperatures higher than those present in the prepolymerization zone. For example, the temperature within the finishing zone can be increased to a value within the range of 270 ° C to 305 ° C until the intrinsic viscosity of the melt is increased from the intrinsic viscosity in the prepolymerization zone (typically from 0.20 to 0.30 dL / g but often no more than 0.48 dL / g) for an intrinsic viscosity in the range of 0.54 dL / g to 1.2 dL / g. The final vessel, commonly known in the industry as a “high polymerizer”, or “finisher”, is often operated at a pressure lower than that used in the prepolymerization zone, for example, within a range between 0.2 and 4.0 torr ( 0.03 to 0.53 kPa). Although the finishing zone typically involves the same basic chemicals as the prepolymer zone, the fact that the size of the molecules, and consequently the viscosity differ, means that the reaction conditions also differ. However, like the prepolymer reactor, each of the finishing vessel (s) is operated under vacuum or with inert gas, and each typically has some type of mixture or renewed surface to promote the removal of ethylene glycol.

According to the present invention, at least one additive compound comprising a catalyst deactivating compound is added for the melting of polyester polymer after said melting of polyester polymer has achieved an intrinsic viscosity of at least 0.45 dl / g , or at least 0.55 dL / g, or at least 0.55 dL / g, or at least 0.60 dL / g, or at least 0.65 dL / g, or at least 0.68 dL / g , or at least 0.70 dL / g, or at least 0.72 dL / g, or at least 0.74 dL / g, or at least 0.76 dL / g, or at least 0.80 dL / g. The addition of the catalyst deactivator desirably occurs near the discharge of the polycondensation finishing zone or just after it but before cutting, although the addition of catalyst deactivator can occur at any point within the melting phase consistent with a polymer melt. polyester with a sufficiently high value of intrinsic viscosity.

Stabilization or deactivation of catalyst at or near the end of a melt process is optionally followed by an optional build-up of intrinsic viscosity followed by the production of polyester particles after solidification of the polyester polymer melt. There are many desirable characteristics for the melting of polyester polymer and for the subsequent solid polyester particles produced.

For example, a normally desirable characteristic of polyester is a low concentration of residual or free AA in the solid polyester particles and a low generation rate when melting said particles. For example, in carbonated soft drink (“CSD”) and water applications, polyester particles and more specifically PET polyester granules are often formed within the bottle preforms. The AA that is released during the formation of bottle preforms can impart a noticeable and possibly undesirable taste to the drink. Acceptable AA concentrations may vary among possible applications for the polymer.

An advantage of this invention is the ability to produce a polyester polymer in which the AA generation rate in polyethylene terephthalate polymers is low enough to be acceptable in water bottle applications while at the same time having the required intrinsic viscosity in applications of CSD bottles, therefore a dual-use resin.

Another example of a common desirable characteristic of the polyester polymer melt and any subsequent polyester particles produced by the melt solidification is the low concentration of vinyl terminals. Vinyl terminals as represented by the formula: CO₂-CH = CH₂ are known precursors to AA. A commonly accepted mechanism whereby AA is generated in fused polyester containing ethylene glycol residues in at least some of the repeating units is by splitting the inner chain of a polyester polymer chain to form a vinyl end group (VEG) and a carboxylic acid terminal group. The VEG can react with a hydroxyethyl terminal group (HEG) to form free or residual AA and a new internal ester bond. There is a common perception that a strong concentration of vinyl terminals is thus undesirable because of the vinyl terminal's ability to react and form AA during subsequent melt processing of solid polyester polymer particles. For example, AA can not only form during the process of making the melting phase of polyester polymers but can also occur during injection molding using PET particles (for example, granules) to manufacture bottle preforms. An advantage of the present invention is the production of a polyester polymer that eliminates the need to add an AA remover or other additive to decrease AA before or during injection molding of PET preforms or melt processing in other articles. In addition, there is a general tendency to operate polyester polymerization processes in the melt phase at low temperatures and low production rates to inhibit subsequent generation of AA in downstream processing applications. Another advantage of the present invention is that this general trend is no longer as critical.

In addition, US 5,852,164 indicates that the concentration of terminal groups or olefin terminals, which is the sum of the vinyl terminals, vinylidene terminals, and the methyl cyclohexene terminals, is preferred to be less than 25 eq / ton in order to improve the melt heat stability of highly modified polyester polymers, which contain in almost all examples about 33 mole% 1,4-cyclohexanedimethanol, based on the total diol content. In general, it is undesirable, especially in molding processes, that the intrinsic viscosity of the polymer decreases upon heating as the properties or part of the resulting article will be negatively impacted. For example, in the production of bottles and / or preforms that are typically manufactured without the addition of modifiers (unmodified) or slightly modified polyester polymer, and in particular beverage bottles such as carbonated soft drinks or water bottles made from of the particles of the invention and the difference in intrinsic viscosity between the intrinsic viscosity of the particles and the intrinsic viscosity of the preforms and / or bottles is often not more than 0.04 dL / g, preferably not more than 0.03 dL / g, and more preferably not more than 0.02 dL / g. Additionally, it is known that vinyl terminals can also polymerize under extreme conditions in polyvinyl esters which can be responsible for the yellow color of PET.

However, applicants have surprisingly found that the addition of a catalyst deactivator leads to the production of a polyester polymer and subsequent polyester particles with a relatively strong concentration of vinyl terminals in the polymer and comparatively a low AA generation rate at the melting temperatures ; where the concentration of vinyl terminals has no appreciable negative impact on the quality of the polyester polymer. In addition, there is an embodiment, in which lower levels of AA generation or AA preform are not required, which allows for a shorter duration polycondensation or faster production rate and creates a viscous product appropriate intrinsic treatment without solid state treatment.

The polyester polymer can also contain a catalyst deactivator. By a catalyst deactivator we mean an effective compound to at least partially deactivate or inhibit the activity of the catalyst system. A compound is effective to at least partially deactivate the catalyst system when adding it at a given level, and alone to test the effectiveness of a compound at a given level, when one or both a) the rate of solid state treatment under real operating conditions it is reduced with respect to the same polymer without the deactivator (“case without additive”) and / or b) when added earlier, the polycondensation rate of the melting phase under real operating conditions for a constant intrinsic viscosity target is reduced, that is, it takes longer to reach the intrinsic viscosity target, or the polymer's intrinsic viscosity is reduced in constant time with respect to to the case without additive. Preferably, the catalyst deactivator also reduces the rate of AA generation when melting the particles, with respect to the case without additive, to decrease the contribution of AA generation to AA levels in a molded article, such as a preform , in relation to the case without additive, and more preferably this lower amount of AA generated occurs when melting the polyester particles having an intrinsic viscosity of at least 0.72 dL / g obtained from the polymerization of the melting phase.

The catalyst deactivator is added last during the process for the manufacture of the polymer melt in order to limit the activity of the catalyst system during subsequent melt processing steps, in which the catalyst system could otherwise catalyze the conversion of acetaldehyde precursors present in the polymer particles to acetaldehyde and / or catalyze the formation of more AA precursors and their subsequent conversions into AA. Left untreated, the polymer would have a high rate of acetaldehyde generation during extrusion or injection molding, thus contributing to an increase in AA levels in articles manufactured from melting. The stabilizer or deactivator can also help to thermally stabilize the polymer melt near the end of the melt phase polycondensation and during the subsequent melt of polyester particles, which occurs, for example, during melt processing of articles, without the which it is possible that more reactions could occur to cleave the polymer chains in the highly viscous fusion, a way to form more precursors of AA and essentially more AA. Any side reaction at least partially catalyzed by the polycondensation catalyst system can be less of a problem when the polycondensation catalyst system is at least partially deactivated. The catalyst deactivation is not added together with the addition of aluminum compounds or alkali metal compounds or alkaline earth metal compounds or alkali compounds, it is not added at the beginning of the polycondensation because it could inhibit the catalytic activity of the metal catalysts and consequently, the rate of polycondensation. It should be noted, however, that not all types or forms of phosphorus compounds are deactivators, and if they are not, they can, if desired, be added together with the catalyst or at the beginning of the polycondensation.

Suitable deactivating compounds are preferably phosphorus-containing compounds. Phosphorus compounds contain one or more phosphorus atoms. Preferred are phosphate triesters, acidic phosphorus compounds or their ester derivatives, and amine salts of compounds containing acidic phosphorus. Acidic phosphorus compounds have at least one oxy acid group, that is, at least one phosphorus atom with double bond for oxygen and single bond for at least one OH or hydroxyl group. The number of acidic groups increases as the number of hydroxyl groups, attached to the phosphorus atom that is double-bound to oxygen, increases.

Specific examples of phosphorus compounds include, phosphoric acid, pyrophosphoric acid, phosphoric acid, polyphosphoric acid, carboxyphosphonic acids, alkylphosphonic acids, phosphonic acid derivatives, and each of its acidic salts and acidic esters and derivatives, including acidic phosphate esters such as mono- and di-phosphate esters, and non-acidic phosphate esters (for example, phosphate tri-esters) such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tris (2-ethylhexyl) phosphate, oligomeric phosphate triesters, trioctyl phosphate, triphenyl phosphate, tritolyl phosphate, ethylene glycol (tris) phosphate, triethyl phosphonoacetate, dimethyl methylpropionate methylenediphosphonate, mono-, di, and tri-esters of phosphoric acid with ethylene glycol, diethylene glycol, or 2-ethylhexanol, or mixtures of each. Other examples include distearylpentaerythritol diphosphite, mono- and dihydrogen phosphate compounds, phosphite compounds, certain inorganic phosphorus compounds that are preferably soluble in polymer melting, poly (ethylene) hydrogen phosphate, and silyl phosphates. Turbidity in particulate solutions or in molded parts is an indication of lack of solubility or limited solubility of an additive in polymer melting. Soluble additives are more likely to deactivate / stabilize the catalyst system. In addition, turbidity in molded parts is undesirable if it exceeds acceptable limits and / or is detrimental to the visual appearance of the molded part.

Other phosphorus compounds that can be added include the amine salts of acidic phosphorus compounds. The amines can be cyclic or acyclic, can be monomeric, oligomeric, or polymeric, and should be selected to minimize turbidity and / or maximize solubility when these are the issues. The organic constituents of the amine can in principle be any organic group. Ammonia and related compounds of the ammonium hydroxide type are appropriate.

Suitable organic groups on the amine include straight and branched alkyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroaryl, etc. Each of these types of organic groups can be substituted or unsubstituted, that is, with hydroxy, carboxy, alkoxy, halo, and the like groups. The organic groups can also contain carbonate, keto, ether, and thioether bonds, as well as amide, ester, sulfoxide, sulfone, epoxy, and the like. This list is illustrative and not limiting.

Preferred amines are cyclic amines having a 5- to 7-membered ring, preferably a six-membered ring. These rings can form a single “monomeric” species, or they can be part of a larger polymer or oligomer.

Preferred cyclic amines are hindered amines that have substituted organic groups at the positions of the ring adjacent to the nitrogen ring. The nitrogen ring itself can also be replaced, that is, with alkyl, aryl, aralkyl, alkaryl, and others. The hindered amines can also comprise a portion of an oligomeric portion or polymeric portion.

Another preferred type of amines are amino acids. Amino acids with points of decomposition at or above polymerization temperatures are especially preferred. L-enanciomer, Denanciomer or any mixture thereof, including racemic mixtures, may be used. The amine group and the carboxylic acid group do not have to be attached to the same carbon. Amino acids can be alpha, beta or gamma. Substituted amino acids can be used. Amino acids with some solubility in water are especially preferred since this allows the synthesis of salt to be made in water, that is, without VOC's (volatile organic compounds).

Appropriate amines contain at least one hydrogen capable of forming salt with an acid containing phosphorus. In hindered amines containing portions of N-alkylated piperidinyl, for example, salt formation can involve piperidinyl nitrogen, generating species such as (but not limited to):

O

<img file="BRPI0806626A2_D0002.tif" />

When there is nitrogen in the amine compound that can form salt, one mole of acid containing phosphorus is used per mole compound of amine. When there are two or more nitrogen atoms in the amine compound that can form salts, two or more moles of acid can be used per mole of amine compound, up to an amount of acid, which creates salts with no remaining neutralizable nitrogen, or slightly in excess of this quantity.

The carboxylic acid group of the amino acid opens the possibility that the amine portion of the salt can be reacted within the polyester chain. The reaction within the polyester chain could result in less volatility and less extractability. The reaction within the polyester chain can also be carried out if the amine portion of the salt contains a hydroxyl and / or carboxyl group. If there is only 1 hydroxyl or carboxyl group, the salt could act as a terminator. If there are a total of 2 or more reactive groups (carboxyl or hydroxyl), the salt may not always be at the end of the chain. The reaction within the polyester chain is also possible for the phosphorus-containing portion of the salt. For example, phosphoric acid can react with hydroxyl compounds to form phosphate esters. The end of the polyester chain is often an end group r

hydroxyethyl. Phosphoric acid can also react in the middle of the polyester chain.

The precursor to the phosphorus portion of the phosphorus salt can be any phosphorus oxy acid including but not limited to hypophosphorous acid, phosphorous acid, phosphoric acid, polyphosphoric acid, polyphosphoric acids, pyrophosphoric acid, phosphoric acids, phosphonic acids, phosphate monoesters, phosphate diesters, phosphonate monoesters, pyrophosphate monoesters, pyrophosphate diesters, pyrophosphate triesters, or salts or compounds that still contain at least one acidic hydrogen, etc. Hydrogen or any OH group attached directly to the P = O group is acidic. Compounds with more than one acidic hydrogen can have one or more acidic hydrogens replaced by organic groups such as alkyl, aryl, aralkyl, alkaryl, etc., through polyether oligomers, polyester oligomers, etc. However, at least one acidic hydrogen forming salt must remain. Phosphorus oxyacids with one or more hydrogen attached directly to the P = O group can have one or more of these hydrogens replaced with organic groups such as alkyl, aryl, aralkyl, alkaryl, etc. Examples of these compounds include, but are not limited to, alkylphosphonic acids, alkylphosphonic acids and dialkylphosphonic acids. As with amines, organic groups can be replaced.

In one embodiment, salts are prepared by reacting one or more compounds containing acidic phosphorus with one or more basic organic compounds containing nitrogen, wherein the compounds containing phosphorus are preferably selected from compounds having the formulas:

í?

(t) R_rO — P — OH

O ^r2 roi ^ h =?

R, -0 (3) R—

The f

Rg

XX o *, 0

H) X, _v

X Ô— '^ 0 X (5) HO-pf ^ VoH _O_y \ _o where Ri and R₂ are independently selected from hydrogen, Cr C₂₂ alkyl, C_rÇ₂₂ substituted alkyl, C₃-Cs cycloalkyl, substituted C3-C8 cycloalkyl, heteroaryl, and aryl;

n is 2 to 500; ex is selected from hydrogen and hydroxy; and in which the basic organic compounds containing nitrogen are preferably selected from the compounds having the formula:

0)

<img file="BRPI0806626A2_D0003.tif" />

<img file="BRPI0806626A2_D0004.tif" />

(4)

<img file="BRPI0806626A2_D0005.tif" />

<img file="BRPI0806626A2_D0006.tif" />

^ 10 &lt;«» R, a ^ tj Lj,

<img file="BRPI0806626A2_D0007.tif" />

<img file="BRPI0806626A2_D0008.tif" />

(19)

<img file="BRPI0806626A2_D0009.tif" />

(20)

<img file="BRPI0806626A2_D0010.tif" />

on what:

R, and R₂ are independently selected from hydrogen, C1-C22 alkyl, C_rÇ₂₂ substituted alkyl, C3-C8 cycloalkyl, C₃Ç₈ substituted cycloalkyl, heteroaryl, and aryl;

Each of the following types of organic groups can be substituted or unsubstituted, that is, with hydroxy, carboxy, alkoxy, halo and / or similar groups, and any combination thereof. The organic groups can also contain carbonate, keto, ether, and thioether bonds, as well as amide, ester, sulfoxide, sulfone, epoxy, and the like. This list is illustrative and not limiting.

R3, R4, and R5 are independently selected from hydrogen, Ci-C₂₂ alkyl, C_rÇ₂₂ substituted alkyl, C₃-Ç₈ cycloalkyl, and C3C₈ substituted cycloalkyl where preferably at least one of R₃, R4, and R₅ it is a substituent other than hydrogen; however, in the case where R₃, R4, and R₅ they are all hydrogen, ammonium hydroxide is the preferred form; R₃ and R4, or R4 and R₅ collectively they may represent a divalent group forming a ring with the nitrogen atom to which they are attached, for example, morpholino, piperidine and the like;

R ^, R7, Rs and R₉ are independently selected from hydrogen, Ci-C₂₂ alkyl, Ci-C₂₂ substituted alkyl, C₃-Ç₈ cycloalkyl, C₃Ç₈ substituted cycloalkyl, heteroaryl, and aryl;

Rio is selected from hydrogen, -OR ^, C_rÇ₂₂ alkyl, C_rÇ₂₂ substituted alkyl, C₃-Ç₈ cycloalkyl, C₃-Ç₈ substituted cycloalkyl;

Rn is selected from hydrogen, C_rÇ₂₂ alkyl, C_rÇ₂₂substituted alkyl, C₃-Ç₈ cycloalkyl, C₃-Ç₈ substituted cycloalkyl, heteroaryl, aryl, -Y1-R3 or a succinimido group having the formula

<img file="BRPI0806626A2_D0011.tif" />

on what

Laugh₂ is selected from hydrogen, Ci-C₂₂ alkyl, C_rÇ₂₂substituted alkyl, C₃-Ç₈ cycloalkyl, C₃-Ç₈ substituted cycloalkyl, heteroaryl, aryl and may be located at positions 3, 4 or 5 in the aromatic ring;

the group -N (R₃) (R4) can be located at positions 3, 4 or 5 on the piperidine ring of the nitrogen compound (5).

-CO groups₂R₃ and Rj can be located in any of the positions 2, 3, 4, 5, 6 of the nitrogen compound's piperidine ring (6).

Lj is a divalent bond group selected from C₂-Ç₂₂alkylene, - (CH₂CH₂-Yi) i-₃-Ch₂CH₂-; Ç₃-C8-cycloalkylene; arylene; or -COL₂-OC-;

L₂ is selected from Ci-C₂₂-alkylene, arylene, - (CH₂CH₂Yi) i-3-CH₂CH₂- and C₃-C8-cycloalkylene;

Yi is selected from -OC (O) -, -NHC (O) -, -O-, -S-, -N (Ri) -; Y₂ is selected from -O- or -N (Ri) -;

Laugh₃ and R14 are independently selected from -OR₂ and N (R₂)₂;

Z is a positive number up to about 20, preferably up to about 6;

ml, is selected from 0 to about 10;

nl is a positive number selected from 2 to about 12;

R15 and Riô are independently selected from hydrogen, C_rÇ₂₂ alkyl, C_rÇ₂₂ substituted alkyl, C₃-Ç₈ cycloalkyl, C₃Ç₈ substituted cycloalkyl, heteroaryl, aryl, and radical A in which radical A is selected from the following structures:

<img file="BRPI0806626A2_D0012.tif" />

Radical A structures where * designates the position of the fixation.

Preferably at least one of Ri₅ and Ri6 is a Radical A; and wherein the ratio of number of phosphorus atoms in the acid-containing phosphorus compound to the number of basic nitrogen atoms in the basic organic compound is about 0.05 to about 2, preferably about 0.25 to about 1 ,1.

The term "C1-C22 alkyl" denotes a saturated hydrocarbon radical that contains from one to twenty-two carbons and that can be a straight or branched chain. Such C1-C22 alkyl groups can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, tertbutyl, neopentyl, 2-ethylheptyl, 2-ethylhexyl, and the like.

The term "C1-C22 substituted alkyl" refers to C1-C22 alkyl radicals as described above that can be substituted with one or more substituents selected from hydroxy, carboxy, halogen, cyano, aryl, heteroaryl, C₃-Ç₈ cycloalkyl, C₃-Ç₈ substituted cycloalkyl, Ci-C₆ alkoxy, Ci-Ce alkanoyloxy and the like.

The term “C₃-Ç₈ cycloalkyl ”is used to denote a cycloaliphatic hydrocarbon radical containing three to eight carbon atoms. The term “C₃-Ç₈ substituted cycloalkyl ”is used to describe a C radical₃Ç₈ cycloalkyl as detailed above containing at least one group selected from Ci-Cô alkyl, Ci-Cô alkoxy, hydroxy, carboxy, halogen, and the like.

The term "aryl" is used to denote an aromatic radical containing 6, 10 or 14 carbon atoms in the conjugated aromatic ring structure and these radicals are optionally substituted with one or more groups selected from Cq-Có alkyl; Ci-Cô alkoxy; phenyl, and phenyl substituted with Cj-Có alkyl; Cj-Cô alkoxy; Ç₃-Ç₈ cycloalkyl; halogen, hydroxy, carboxy, cyano, triofluoromethyl and the like. Typical aryl groups include phenyl, naphthyl, phenylnaphthyl, anthryl (anthracenyl) and the like. The term "heteroaryl" is used to describe conjugated cyclic radicals containing at least one heteroatom selected from sulfur, oxygen, nitrogen or a combination of these in combination with two to about ten carbon atoms and these heteroaryl radicals replaced with the groups mentioned above as possible substituents on the aryl radical. Typical heteroaryl radicals include: 2- and 3-furyl, 2- and 3-thienyl, 2- and 3-pyrrolyl, 2-, 3-, and 4-pyridyl, benzothiophen-2-yl; benzothiazol-2-yl, bezoxazol-2-yl, benzimidazol2-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiazol-2-yl, 1,2,4-thiadiazole-5- useful, isothiazol-5-yl, imidazol-2-yl, quinolyl and the like.

The terms “Ci-C₆ alkoxy ”and“ CrC₆ alkanoyloxy ”are used to represent the groups -O-Ci-Có alkyl and -OCOCi-Cô alkyl, respectively, where“ Ci-Cô alkyl ”denotes a saturated hydrocarbon containing from 1 to 6 carbon atoms, which can be a straight or branched chain, which can be substituted with one or more groups selected from halogen, methoxy, ethoxy, phenyl, hydroxy, carboxy, acetyloxy and propionyloxy. The term "halogen" is used to represent fluorine, chlorine, bromine and iodine; however, chlorine and bromine are preferred.

The term “C₂-Ç₂₂-alkylene ”is used to denote a divalent hydrocarbon radical that contains from two to twenty-two carbons and that can be a straight or branched chain and that can be substituted with one or more substituents selected from hydroxy, carboxy, halogen, Ci-C₆alkoxy and Ci-Cô alkanolyloxy and aryl. The term "Cs-Cs-cycloalkylene" is used to denote divalent cycloaliphatic radicals containing three to eight carbon atoms and these are optionally substituted with one or more "Ci-Cô-alkyl" groups. The term "arylene" is used to denote radicals 1,2-, 1,3-, and 1,4-phenylene and these optionally substituted with Ci-C₆-alkyl, Ci-C₆alkoxy and halogen.

Preferred hindered amines contain alkyl substituted piperidinyl moieties and / or triazine moieties, more preferably hindered amines where at least one amine group is replaced by both a triazine moiety and an alkyl substituted piperidine moiety. In the most preferred hindered amines, portions containing amine group are linked by an alkylene group, preferably a (-CH2-) group_n where n is 2 to 12, preferably 4 - 10, and more preferably 6 or 8. The most preferred hindered amine is Cyasorb® UV-3529, containing repeat units of the formula:

<img file="BRPI0806626A2_D0013.tif" />

The salt of the amine component can be prepared by bringing together the compound containing acidic phosphorus and the organic compound containing basic nitrogen or ammonium hydroxide in an appropriate manner. An appropriate way is any procedure that involves contacting the acid containing acidic phosphorus with the basic organic compound or ammonium hydroxide. For example, the compound containing acidic phosphorus and the organic compound containing basic nitrogen or ammonium hydroxide can be dissolved in appropriate solvents, and the solutions mixed, followed by precipitation of the reaction product; mixing the acid containing phosphorus and the basic organic compound or ammonium hydroxide without solvent; and the like.

The ratio of the number of acidic groups in the acidic phosphorus compound to the number of basic nitrogen atoms in the basic organic compound or ammonium hydroxide can be in the range of about 0.05 to about 2, preferably 0.25 to about of 1.1. Compositions containing a large excess of unreacted acidic phosphorus compounds can result in corrosion of the process equipment during the manufacture of polyester, manufacture of the concentrate (if any) or manufacture of the preform.

Since the catalyst system used in the invention can be so easily at least partially deactivated, phosphorus compounds previously found to be less effective with antimony catalyzed systems, such as the complete esters of acidic phosphorus compounds, of the triester type of phosphate, can now be used effectively in the polymer melt and process of the invention. Furthermore, it has been found that phosphorus compounds that cause an increase in turbidity with antimony catalyzed systems, such as phosphorous acid, can be used as a deactivator with the catalyst system of the present invention without acting to increase turbidity due to reduction to a metal, which in the case of catalyzed systems with antimony, gives a gray or black color to the polyester. The amount of phosphorus compound or other catalyst deactivator used in this process is effective in reducing the amount of AA generated when melting the polymer particles, which are produced through the process of making the melting phase, partially or completely deactivating the catalytic activity of the combination of titanium catalysts or said residues of aluminum atoms (i) and alkaline earth metal atoms or alkali metal atoms or alkali compound (ii). The amount of AA generated during the merger that can be tolerated depends on the end use of the application and often on the owner of the new beverage brand involved. Preforms used to make water bottles often have lower specifications for AA than preforms used for carbonated soft drinks (CSD). For example, the maximum acceptable level of AA in CSD preforms can be about 8 ppm, while the maximum acceptable level of AA in some water preforms can be about 3 ppm. Preforms designed for use in both water and CSD markets, dual use preforms, often have specifications similar to AA to preforms used only in the water market. The amount of phosphorus compound or other catalyst deactivator used depends on the target on the polyester, which depends on the end use application and / or the owner of the new brand of beverage involved. For example, the marked level of phosphorus in PET will be higher for water or dual use applications than for CSD applications. Since the last addition of catalyst deactivator can cause loss of intrinsic viscosity, the minimum possible amount of deactivator should be added to achieve the marked level of AA in the part for a given application. If the deactivator is corrosive, this is another reason to use the minimum possible amount of catalyst to reach the marked level of AA in part of a given application.

In the case where an aluminum compound and / or an alkali metal compound and / or an alkaline earth compound is used to catalyze the polycondensation, the cumulative amount of aluminum, alkali or alkaline earth metals, and any other catalyst metals are taken into account present in the merger. The ratio of moles of phosphorus to the total moles of aluminum and alkaline earth metal and / or alkali metal (P = M MR where M is considered to be the sum of moles of aluminum, the moles of alkaline earth metals, if present and the moles of alkali metals, if present, where MR for molar ratio) is generally at least 0.1: 1, or at least 0.3: 1, or at least 0.5: 1, or at least 0.7: 1, or at least 1: 1 , and up to about 5: 1, or more preferably, up to about 3: 1, or up to 2: 1, or up to 1.8: 1, or up to 1.5: 1. Excessively large amounts of phosphorus compounds should be avoided to minimize the loss in the polymer's intrinsic viscosity when adding the phosphorus compound to the polyester melt. In addition, in the case of aluminum and alkali metal catalysts, there is an optimal amount of phosphorus to obtain the least amount of AA generated; for this reason, excess phosphorus compounds, especially if they are acidic, can increase the amount of AA generated. The preferred range for P: M MR is 0.5 to 1.5.

Metal compounds other than aluminum, alkali metals and alkaline earth metals can also react with phosphorus compounds. If, in addition to aluminum compounds, alkali metals and / or alkaline earth metals, other metal compounds that react with phosphorus compounds are present, then the amount of phosphorus compound added later is desirably in excess of that required to achieve P : M MR marked to ensure that phosphorus compounds react or combine with all reactive metals present. In another embodiment of the invention, the polyester polymer composition contains aluminum atoms within a range of 5 ppm to 100 ppm, or 7 to 60 ppm, or 8 ppm to 20 ppm, based on the weight of the polymer of polyester, and the molar ratio of all alkaline earth metal and / or alkali metal atoms to the moles of aluminum atoms is within a range of 0.5: 1 to 6: 1, or 1: 1 to 5: 1, or 2 : 1 to 4: 1, and the P: M ratio is in the range of 0.1: 1 to 3: 1, or 0.3: 1 to 2: 1, or 0.5: 1 to 1.5: 1. Preferably, the polyester polymer composition contains aluminum and at least one of lithium or sodium or potassium or a combination thereof. In one embodiment, the composition contains aluminum and lithium, or aluminum and sodium atoms.

In the case of a titanium polycondensation catalyst, in which the catalyst deactivator comprises a phosphorus compound, in another embodiment of the invention, the deactivator is present in a P: Ti (from P: Ti) molar ratio of at least 0.015: 1, or at least 0.7: 1, or at least 1: 1.

In another embodiment, a desirable range of titanium atoms is about 2 to about 20 ppm based on the weight of the polyester, or about 4 ppm to about 15 ppm, or about 5 ppm to about 10 ppm.

Since one of the benefits of the invention is the ease with which the catalyst system can be deactivated, care must be taken not to add the phosphorus compound or other deactivator too soon as this would slow the rate of polycondensation. The addition of the desired final amount of phosphorus should be completed only after substantial completion of the polycondensation and thereafter, and preferably, the desired final amount of phosphorus compound should not be added for the polymer melting in the manufacturing process of the phase in question. fusion until substantial completion of polycondensation and thereafter.

In embodiments in which phosphorus compounds are added in the melt phase polymerization, with the final amount of phosphorus we mean the desired final amount of phosphorus in the polyester polymer leaving the melt phase manufacturing process or as appearing in a granule. If desired, a partial amount of phosphorus compound can be added earlier in the melting phase manufacturing process, such as at the beginning of the polycondensation, providing that a portion of phosphorus representing the final amount is added later in the course of the polycondensation or thereafter onwards, but before solidification as explained below. To maximize the rates of polycondensation and / or production, most, or preferably the bulk, or more preferably all of the phosphorus compound is added afterwards to the melting phase manufacturing process. For those skilled in the art, it is known that processes involving ester exchange may require the addition of a phosphorus compound immediately following the ester exchange to deactivate the ester exchange catalyst. If the ester exchange catalyst is also provided as at least part of the catalysis in the polycondensation zone, the addition of phosphorus after the ester exchange is omitted.

To minimize the loss of intrinsic viscosity if large amounts of phosphorus are added, or to further minimize the potential for loss of intrinsic viscosity even if moderate or optimal amounts of phosphorus are added, it is desirable to add the pure phosphorus compound, that is, without further dilution, as in the case of 85% or more phosphoric acid. If a vehicle is used, it is preferred that the vehicle is non-reactive, that is, it does not break the polymer chain or increase AA generation rates. Water, alcohols, glycols and PET with lower molecular weight are known to break the polymer chain. Since the minimum amount of phosphorus compound and the associated loss of intrinsic viscosity are known, the melting phase process can be carried out so that the intrinsic viscosity, manufactured before deactivation / stabilization, is greater than the amount of loss of intrinsic viscosity expected so that the intrinsic viscosity target can be achieved.

Once the desired viscosity is obtained in the finisher zone and the deactivator is added afterwards, the melt is usually processed to convert the melt PET into amorphous solid granules. Typically, the weight of a single amorphous solid granule would be in the range of 0.01 to 10 grams. An appropriate intrinsic viscosity of the melting phase can be in the range of 0.5 dL / g to 1.2 dL / g. However, an advantage of the present process is that the solid state treatment step can optionally be avoided. Solid state treatment is commonly used to increase the molecular weight (and intrinsic viscosity) of the granules in solid state treatment, often by at least 0.05 units, and more typically from 0.1 to 0.5 units.

The method and equipment for converting melt polymer out of the melt phase reactors into granules is not limited, and any conventional system used for granule making is appropriate in the practice of the invention. For example, strands of the polyester polymer melt are cooled at least on the surface to below the polymer glass transition temperature to form a cooled polyester polymer, followed by pelletizing of the cooled polyester polymer to form solid amorphous granules. These granules can optionally be crystallized. Alternatively, the molten polymer can be extruded through a mold and immediately cut into granules before the polyester polymer cools below its glass transition temperature. These granules can optionally be crystallized before the polymer cools below its glass transition temperature.

It should be noted that for some crystallization of polyester polymers and / or "solid state treatment" it can be very difficult. For example, PET comprising copolymerized cyclohexanomethanol (CHDM) in amounts of 15 or more weight percent diol component is amorphous or has a low crystalline percentage (for example, less than 1% crystalline or less than 5% crystalline or less than 10% crystalline). For this reason, in an embodiment of the invention, especially with reference to solid polyester polymer particles, said particles are limited to those combinations of copolymerized materials (for example, diacids and diols) that can be quickly completely crystallized, typically with a percentage of crystallinity of at least 10% or at least 20%.

In a preferred embodiment, the purpose of the process differs substantially from previous processes in that it is capable of producing a product with inherently high enough viscosity directly in the melting phase, without involving any need for subsequent solid state polymerization, often called “Solid state treatment”. Failure to perform the solid state treatment may also allow direct molding from the melt. These advantages are achieved through the use of at least one polycondensation catalyst in conjunction with a catalyst deactivator, such as phosphoric acid or amine salts of phosphorus-containing acids, which are added later in the polycondensation stage. It was surprisingly found that the present method can allow for a reduced polycondensation time, create a product with appropriate inherent viscosity without solid state treatment, and produce a solid product exhibiting reduced residual acetaldehyde content in the solid polyester particles, reduced generation of acetaldehyde when fusing and relatively strong concentration of vinyl terminals.

The solid particles produced in the melting phase process preferably have an acetaldehyde generation rate, when measured in a plastometer for extrusion at 295 ° C for 5 minutes, 20 ppm or less, or 18 ppm or less, or 16 ppm or less, or 13 ppm or less, or 11 ppm or less, or 10 or less, or 8 or less. The process of the invention does not require melting the particles at 295 ° C for 5 minutes to manufacture molded articles. In the case of measuring the rate of acetaldehyde generation in preform, it is sufficient to use the ASTM # method as described above without subjecting the preforms to an additional melting history since due to manufacturing a preform, the granules are melted in an extruder before injection molding. When the polyester particles are fed to an extruder, which is part of an injection molding machine, preforms of 566.99 g made from solid polyester particles of the invention have an AA level of 10 ppm or less , 8 ppm or less, 6 ppm or less, 5 ppm or less, or 4 ppm or less under any manufacturing conditions, but for the purposes of determining the level of AA generation, the level is determined with a drum temperature of 285 ° C and a melting residence time of about 2 minutes.

The solid particles produced in the melting phase manufacturing process preferably have a vinyl terminal concentration of 8 peq / g or more, or 1.0 peq / g or more, or 2.0 peq / g or more, or 3, 0 small / g or more, or 5 small / g or more.

The particles of the invention are directly or indirectly packaged as a raw material inside containers of r

shipping, which are then shipped to customers or distributors. It is preferred to subject the crystallized particles to any embodiment of the process described here without the polymerization of the particles in the solid state treatment at any point before packing the particles in shipping containers. With the exception of polymerization in solid state treatment, the particles can be subjected to numerous additional processing steps in / between any of the expressed steps.

Shipping containers are containers used for shipping by land, sea or air. Examples include railway wagons, semi-motorized trailer containers, Gaylord boxes, ship hulls, or any other container that is used to transport finished polyester particles to a customer. Customers are typically converting entities that convert particles into preforms or other shaped articles.

The shipping containers contain a raw material of polyester particles. The raw material occupies a volume of at least 3 cubic meters. In preferred embodiments, the raw material in the shipping container occupies a volume of at least 5 cubic meters, or at least 10 cubic meters. Typically, the individual weight of a finished polyester particle would be in the range of 0.01 to 10 grams.

In one embodiment, finished polyester polymer particles having an average intrinsic viscosity of 0.68 dL / g, or 0.70 dL / g, or 0.72 dL / g, or 0.74 dL / g , or 0.76 dL / g, or 0.80 dL / g, obtained in a melt phase polymerization and a residual acetaldehyde level of 10 ppm or less, or 5 ppm or less; wherein said particles comprise an aluminum level in an amount of 3 ppm, or at least 5 ppm, or at least 8 ppm, or at least 11 ppm, or at least 15 ppm, based on the weight of the polymers. Preferably, the polyester particles in the shipping container also have a vinyl terminal concentration of 8 ppm / g or more, or 1.0 ppm / g or more, or 2.0 ppm / g or more, or 3.0 ppm / g or more, or 5 peq / g or more. Preferably, the polyester particles in the shipping container also have a degree of crystallinity of at least 20%, preferably at least 30%; and the particles also contain a non-zero level of an alkaline earth metal or alkali metal, along with a non-zero level of phosphorus. More preferably, the AA generation of such particles is less than 20 ppm, or less than 18 ppm, or less than 16 ppm, or less than 14 ppm, or less than 12 ppm, or less than 10 ppm, and the particles have an L * gloss of at least 55, or at least 60, or at least 65, or at least 70, or at least 73, or at least 76, and have no

AA. The particles are desirably contained in a shipping container. More preferably, the particles were not polymerized in the solid state treatment. By "finished" particles, we mean particles that have been subjected by the particle manufacturer to all the processing conditions necessary to produce a particle ready to be fed into the dryer hoppers associated with a molding machine or directly to a used molding machine to convert the particles into articles, without any additional processing steps performed by the particle manufacturer.

Molded products can be formed from melt phase products using any conventional techniques known to those skilled in the art. For example, melt phase products, optionally polymerized in solid state treatment, which are crystallized to a degree of crystallization of at least 10%, are fed to a melt extrusion machine and fusion injection molding within models such as such as preforms suitable for stretch blow molding in containers for drinks and food, or an injection molding machine, or a machine to merely extrude into other shapes such as sheets. Suitable processes for forming the products are known and include extrusion, extrusion blow molding, melt casting, injection molding, a melt-to-mold process, stretch blow molding (SBM), thermoforming, etc.

Examples of types of molded products that can be formed from melt phase products and the polyester polymer composition of the invention include sheet; movie; packaging and containers such as preforms, bottles, jars, and trays; stems; tubes; lids; and filaments and fibers. Beverage bottles made of polyethylene terephthalate suitable for containing water or fizzy drinks, heated drink bottles suitable for containing beverages that are placed hot inside the bottles are examples of types of bottles that are made from the crystallized particles of the invention. Examples of trays are those that are double refractory and other CPET trays.

In another embodiment, the molded article preferably does not have an organic acetaldehyde remover. Preferably, ingredients added to the solid polyester particles in the melt processing step do not include organic acetaldehyde removers.

As described above, catalyst deactivators are added later in the course of polycondensation or thereafter but before solidification. It is also possible to add a small amount of deactivator earlier in the melting phase manufacturing process while adding the bulk of deactivator later in the melting phase manufacture. In addition to the embodiment where the total amount of deactivator is added during the melting process for the manufacture of the polyester polymer, in another embodiment, a portion of the total amount of deactivator is added to the polyester polymer in at least minus two stages, once in the melt phase process for making the polyester polymer and again at any point after the polyester polymer is solidified and before the article is formed from the polyester polymer, such as during melt processing of the polymer of polyester to manufacture an article as conventionally made in an extruder or injection molding machine to manufacture the article. In yet another embodiment, the total amount of deactivator is added after solidification and before making the article.

The partial or total addition of phosphorus compound after solidification of the melting phase manufacturing process can be carried out or by performing the melting composition of the catalyst deactivator with the polyester polymer particles to form a solid concentrate of polymer particles of polyester containing randomly dispersed catalyst deactivator compound (s), after which the concentrate is fed to the melt processing zone to manufacture an article together with a feed stream of polyester particles; or a stream of catalyst deactivator compounds can be added directly as a pure stream, or in a slurry or dispersion made with a liquid carrier, along with a stream of polyester polymer particles to the melt processing zone to manufacture the articles. In this way, an embodiment is provided in which crystalline polyester polymers are produced from a melting process without a catalyst deactivator added later, followed by mixing the catalyst deactivator with the polyester polymer through a extrusion by composition or in an extruder portion of the injection molding process such as that used to melt solid, liquid ingredients, or cast within a polyester polymer stream in an extruder, or that used to manufacture an article molded by extrusion in the injection molding process, or by mixing in any other mixing device.

In this embodiment, the mixing device where the catalyst deactivator is introduced can be part of the injection molding process, or it can be a separate step before injection molding. The catalyst deactivator can be introduced neat, in a liquid vehicle or through a polymer concentrate. Pure or liquid vehicle introduction is more preferred since the reaction of the catalyst deactivator with the catalyst in the polymer vehicle can decrease effectiveness. If the catalyst deactivator is a liquid and is added pure or in a liquid vehicle, an ambient mixer could be used to coat the granules with the liquid additive before entering an extruder. If the polymer concentrate route is used, the concentrated granules could be mixed dry under ambient conditions with the granules manufactured exclusively in the melting phase to make a “salt and pepper” mixture. These same comments and approaches also apply to fusion mixing of the catalyst deactivator with granules that have been treated in solid state.

This embodiment is particularly useful if the granules are polymerized in the solid state treatment. The incorporation of the catalyst deactivator in the melting phase may in some cases decrease the rate of solid state treatment. If one wishes to polymerize the polyester granules in the solid state, it is advantageous to add the catalyst deactivator after the granules have undergone a polymerization process in the solid state treatment.

This invention can be further illustrated by additional examples of embodiments thereof, although it should be understood that these examples are included for purposes of illustration only and are not intended to limit the scope of the invention.

Examples

The PET oligomer used as a starting material in Comparative Example 1 and Example 1 has about 94 to 96.5% conversion via proton NMR. The concentration level of isophthalic acid is about 2.0 to 2.2 moles%. The concentration level of diethylene glycol is about 4.6 to 4.8 mole%.

The adjustment between the agitator and the bottle can impact the finisher time required during cycles terminated with torque. A paddle stirrer is selected to have a typical fit with the bottle being used. Before the toothpaste cycle is placed in the jar, which is then equipped with a paddle stirrer, polymer head, teflon tube with a shoulder and hose. The flask is inverted when the stirrer is pushed and turned manually. The light areas on both sides of the center are measured. The width of the light areas should total between 1.7 and 2.7 cm. The bottle is rinsed with water and acetone before use.

For polycondensation, the ground oligomer (103 g) is weighed in a half-liter bottle with a round bottom and a neck selected by the preceding paragraph. The catalyst solution or mixture is added to the flask. The flask is equipped with a 316 L stainless steel paddle stirrer selected by the preceding paragraph and a glass polymer head equipped with a Teflon tube with a shoulder and hose. After attaching the polymer head to a side arm and a purge hose, two nitrogen purges at 0.5 torr (0.07 kPa) are completed.

Polymer discs manufactured in the laboratory are cooled from the outside (where the polymer meets the bottle) to the inside (where the polymer meets the bottle stem; the deepest part of the disc is in the center where the stirrer rod is located). While the polymer discs manufactured in the laboratory are cooled, some generation of AA may occur. In an industrial manufacturing production environment, fused strands or fused globules that become particles or granules are much finer and cool much faster than relatively large discs or are abruptly cooled. The percentage of AA reduction is still of interest as a relative point of comparison since all samples in an example have about the same cooling time.

Comparative Example 1

The oligomer and procedure used are described in the preceding paragraphs of the Examples sections. A 0.94% w / w Sb solution is manufactured from antimony triacetate in ethylene glycol.

Aluminum isopropoxide, titanium hydroxide and ethylene glycol are heated to 125 ° C in an open bottle, which is equipped with a nitrogen purge, a magnetic stir bar and a thermocouple. The mixture is heated for about 3.5 h once 125 ° C is reached. The target level for aluminum is 0.3% by weight, and the target molar ratio Li: Al of 1, 3 or 5. By ICP-OES the mixture with the molar ratio Li: Al of 1 is 0.33% by weight of Al and 0.084% by weight of Li. By ICP-OES, the mixture with the Li: Al molar ratio of 3 has 0.33% by weight of Al and 0.28% by weight of Li. By ICPOES, the mixture with the Li: Al molar ratio of 5 that it is heated for about 3 h, it has 0.38% by weight of Al and 0.45% by weight of Li.

The polymerization reactor is operated according to the CAMILE ™ automation system, programmed to implement the following experimental arrangement. For Sb controls, the temperature for stages 5 - 12 is 280 ° C. For the experimental cycles, the temperature listed in Table 8 is the only one used in the arrangement for stages 5 - 12. The target for aluminum is 10 or 25 or 40 ppm. The target molar ratio Li: Al is 1, 3 or 5.

<td>Internship</td><td>Time (min.)</td><td>Temperature ° C</td><td>Vacuum (torr) (0.13 kPa)</td><td>Agitation (rpm)</td>

<td> 1</td><td> 0,1</td><td> 265</td><td> 730</td><td> 0</td>

<td> 2</td><td> 10</td><td> 265</td><td> 730</td><td> 150*</td>

<td> 3</td><td> 2</td><td> 265</td><td> 330*</td><td> 300*</td>

<td> 4</td><td> 1</td><td> 265</td><td> 330</td><td> 300</td>

<td> 5</td><td> 50</td><td> 285*</td><td> 30*</td><td> 300</td>

<td> 6</td><td> 2</td><td> 285</td><td> 30</td><td> 200*</td>

<td> 7</td><td> 1</td><td> 285</td><td> 30*</td><td> 300</td>

<td> 8</td><td> 20</td><td> 285</td><td> 30</td><td> 200</td>

<td> 9</td><td> 2</td><td> 285</td><td> 4*</td><td> 200</td>

<td> 10</td><td> 60</td><td> 285</td><td> 4</td><td> 200</td>

<td> 11</td><td> 2</td><td> 285</td><td> 0,5*</td><td> 30*</td>

<td> 12</td><td> 500#</td><td> 285</td><td> 0,5</td><td> 30</td>

• = ramp; # = torque termination

The agitation system is automatically calibrated with torque between stages 4 and 5. The finishing stage (# 12) is terminated when the agitator's target torque is reached or exceeded on three separate occasions. No phosphorus compounds are added for any of the cycles in the example.

Table 1

<td>Sample</td><td>Temp. (° C)</td><td>Finisher Time (min.)</td><td>Mean ICP Al (ppm)</td><td>ICP average Li (ppm)</td><td>ICP Li: Al MR average</td><td>IhV (dL / g)</td><td>ItV (dL / g)</td>

<td> 184</td><td> 275</td><td> 278,24</td><td> 11,8</td><td> 2,65</td><td> 0,87</td><td> 0,847</td><td> 0,899</td>

<td> 185</td><td> 285</td><td> 182,83</td><td> 11,7</td><td> 2,65</td><td> 0,88</td><td> 0,88</td><td> 0,936</td>

<td> 196</td><td> 285</td><td> 170,02</td><td> 11,35</td><td> 2,55</td><td> 0,87</td><td> 0,882</td><td> 0,939</td>

<td> 199*</td><td> 275</td><td> 167,72</td><td> 37,1</td><td> 9,9</td><td> 1,04</td><td> 0,897</td><td> 0,956</td>

<td> 5</td><td> 285</td><td> 73,02</td><td> 39,25</td><td> 9,8</td><td> 0,97</td><td> 0,879</td><td> 0,935</td>

<td>* The data c</td><td colspan="2">and PCI reported in -</td><td colspan="5">99 is a unique measurement.</td>

<td>Sample</td><td>ICP Al average (PPm)</td><td>ICP Li: Al MR average</td><td>VEG (small / g)</td><td>AA generation (PP ™)</td>

<td> 184</td><td> 11,8</td><td> 0,87</td><td> 1,1</td><td> 18,12</td>

<td> 185</td><td> 11,7</td><td> 0,88</td><td> 2,3</td><td> 22,11</td>

<td> 196</td><td> 11,35</td><td> 0,87</td><td> 2,1</td><td> 21,89</td>

<td> 199</td><td> 37,1</td><td> 1,04</td><td> 0,2</td><td> 26,14</td>

<td> 5</td><td> 39,25</td><td> 0,97</td><td> 0,2</td><td> 25,04</td>

In the absence of a catalyst deactivator, relatively low levels of Al combined with relatively low molar ratios of Li: AL result in concentrations of vinyl end groups of 8 peq / g or greater and generation of AA at 295 ° C for 5 minutes (Generation from AA

295/5) that is less than or equal to 22 ppm or very close to it. For example, see Samples 184, 185 and 196 in Table 1. At the highest polycondensation temperature of 285 ° C (Samples 185 &amp; 196), the vinyl end groups (VEG) are superior and the generation of AA as well; however, vinyl terminals increase more as a percentage than AA generation. In the three cases (Samples 184, 185 and 196), it can be theorized that the low level of Al and the low molar ratio of Li: Al do not provide sufficient catalytic activity to convert most vinyl terminals to AA; however, the theory is of no connection. For other samples without a catalyst deactivator (Samples 199 &amp; 5), there are higher levels of Al and Li, which can result in sufficient catalytic activity to convert more VEG to AA; for this reason, VEG numbers are less than 0.8 geq / g, and AA 295/5 generation numbers are greater than 22 ppm. The shorter finisher times support the increased catalytic activity of samples manufactured with higher levels of Al &amp; Li. For polymers heated to 275 ° C, the sample manufactured with higher levels of Al &amp; Li (Sample 199) has a finisher time that is about 111 minutes shorter than that of the sample manufactured with lower levels of Al &amp; Li ( Sample 184). For polymers manufactured at 285 ° C, the sample manufactured with higher levels of Al &amp; Li (Sample 5) has a finisher time that is about 103 minutes shorter on average than that of samples manufactured with lower levels of Al &amp; Li Li (Samples 185 &amp; 196).

Example 1

The oligomer and procedure used are described at the beginning of the Examples section. The antimony solution and the aluminum / lithium mixtures used are described in Comparative Example 1. The target for aluminum is 10 or 25 or 40 ppm. The target molar ratio Li: Al is 1, 3 or 5. The molar ratio of phosphorus to metals (P: M MR) is 0, 0.5 or 1, where the moles of metals in the denominator are the sum of the moles of Li plus the moles of Al.

Where P: M MR is not equal to zero in Table 2, 85% phosphoric acid is added in Stage 14 of the next polymerization arrangement. Depending on the target for phosphorus, 85% phosphoric acid is added undiluted for higher targets or as a 50:50 or 1: 1 solution of 85% phosphoric acid and Millipore water for lower targets. An exception is Sample 12 where a ratio of 75:25 phosphoric acid (85%): A Millipore water solution is used.

The polymerization reactor is operated according to the CAMILE ™ automation system, programmed to implement the following arrangement. The temperature listed in Table 2 is the only one used in stages 5 through 16 of the arrangement. The finisher times used in stage 12 are based on the finisher times determined in a similar way to those shown in the Comparative Example

1.

<td>Internship</td><td>Time (min.)</td><td>Temperature (° C)</td><td>Vacuum (torr) (0.13 kPa)</td><td>Agitation (rpm)</td>

<td> 1</td><td> 0,1</td><td> 265</td><td> 730</td><td> 0</td>

<td> 2</td><td> 10</td><td> 265</td><td> 730</td><td> 150*</td>

<td> 3</td><td> 2</td><td> 265</td><td> 330*</td><td> 300*</td>

<td> 4</td><td> 1</td><td> 265</td><td> 330</td><td> 300</td>

<td> 5</td><td> 50</td><td> 285*</td><td> 30*</td><td> 300</td>

<td> 6</td><td> 2</td><td> 285</td><td> 30</td><td> 300</td>

<td> 7</td><td> 1</td><td> 285</td><td> 30</td><td> 200*</td>

<td> 8</td><td> 20</td><td> 285</td><td> 30</td><td> 200</td>

<td> 9</td><td> 2</td><td> 285</td><td> 4*</td><td> 200</td>

<td> 10</td><td> 60</td><td> 285</td><td> 4</td><td> 200</td>

<td> 11</td><td> 2</td><td> 285</td><td> 0,5*</td><td> 30*</td>

<td> 12</td><td>Variable</td><td> 285</td><td> 0,5</td><td> 30</td>

<td> 13</td><td> 3</td><td> 285</td><td> 650*</td><td> 30</td>

<td> 14</td><td> 2</td><td> 285</td><td> 650</td><td> 30</td>

<td> 15</td><td> 1</td><td> 285</td><td> 0,5*</td><td> 45*</td>

<td> 16</td><td> 5</td><td> 285</td><td> 0,5</td><td> 45</td>

• - ramp

The stirring system is automatically calibrated with torque between stages 4 and 5. Calibration with torque means that the antecedent torque, which is the torque before the polymer starts to accumulate appreciably, is determined and subtracted from the measured torque as soon as the polymer increases in molecular weight.

Table 2

<td>Sample</td><td>Relationship Molar Li: Al</td><td>Temp. (° C)</td><td>Relationship Molar Q: M</td><td>Finisher Time (min.)</td><td>ICP Al (ppm)</td><td>ICP Li (PPm)</td><td>ICP Li: Al MR</td><td>ICPP (PPm)</td><td>ICP Q: M MR</td>

<td> 21</td><td> 1</td><td> 275</td><td> 0</td><td> 274</td><td> 9,2</td><td> 2,4</td><td> 1,01</td><td> 0</td><td> 0,0</td>

<td> 71</td><td> 1</td><td> 275</td><td> 1</td><td> 274</td><td> 10,6</td><td> 2,5</td><td> 0,92</td><td> 21,1</td><td> 0,9</td>

<td> 10</td><td> 1</td><td> 285</td><td> 0</td><td> 174</td><td> 9,6</td><td> 2,5</td><td> 1,01</td><td> 3,4</td><td> 0,2</td>

<td> 39</td><td> 1</td><td> 285</td><td> 1</td><td> 174</td><td> 10,8</td><td> 2,5</td><td> 0,9</td><td> 12,9</td><td> 0,5</td>

<td> 49</td><td> 3</td><td> 280</td><td> 0,5</td><td> 182</td><td> 9</td><td> 8</td><td> 3,46</td><td> 26,7</td><td> 0,6</td>

<td> 50</td><td> 5</td><td> 275</td><td> 0</td><td> 189</td><td> 10,9</td><td> 11,4</td><td> 4,07</td><td> 2</td><td> 0,0</td>

<td> 72</td><td> 5</td><td> 275</td><td> 1</td><td> 189</td><td> 13,4</td><td> 11,9</td><td> 3,45</td><td> 55,4</td><td> 0,8</td>

<td> 25</td><td> 5</td><td> 285</td><td> 0</td><td> 90</td><td> 11,4</td><td>n, i</td><td> 3,78</td><td> 1,9</td><td> 0,0</td>

<td> 67</td><td> 5</td><td> 285</td><td> 1</td><td> 90</td><td> 9,5</td><td> 11,1</td><td> 4,54</td><td> 62,4</td><td> 1,0</td>

<td> 66</td><td> 1</td><td> 280</td><td> 0,5</td><td> 143</td><td> 26,3</td><td> 6</td><td> 0,89</td><td> 29,8</td><td> 0,5</td>

<td> 26</td><td> 3</td><td> 280</td><td> 0</td><td> 114</td><td> 21,2</td><td> 17,2</td><td> 3,15</td><td> 1,8</td><td> 0,0</td>

<td> 1</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 23,2</td><td> 19,3</td><td> 3,23</td><td> 50,2</td><td> 0,4</td>

<td> 2</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 24,6</td><td> 19,6</td><td> 3,1</td><td> 61,6</td><td> 0,5</td>

<td> 3</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 24,8</td><td> 19,5</td><td> 3,06</td><td> 59,5</td><td> 0,5</td>

<td> 27</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 24,7</td><td> 18,5</td><td> 2,91</td><td> 46,3</td><td> 0,4</td>

<td> 28</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 22</td><td> 17,7</td><td> 3,13</td><td> 44,7</td><td> 0,4</td>

<td> 29</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 22,8</td><td> 18,3</td><td> 3,12</td><td> 55,3</td><td> 0,5</td>

<td> 57</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 23</td><td> 18,3</td><td> 3,09</td><td> 43,7</td><td> 0,4</td>

<td> 58</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 22,8</td><td> 18,9</td><td> 3,22</td><td> 51,3</td><td> 0,5</td>

<td> 59</td><td> 3</td><td> 280</td><td> 0,5</td><td> 114</td><td> 24,5</td><td> 18,5</td><td> 2,94</td><td> 54,4</td><td> 0,5</td>

<td> 73</td><td> 3</td><td> 285</td><td> 0,5</td><td> 64</td><td> 24</td><td> 18,6</td><td> 3,01</td><td> 47,6</td><td> 0,4</td>

<td> 69</td><td> 5</td><td> 280</td><td> 0,5</td><td> 84</td><td> 25</td><td> 28,4</td><td> 4,42</td><td> 85,4</td><td> 0,5</td>

<td> 20</td><td> 1</td><td> 275</td><td> 0</td><td> 163</td><td> 36,7</td><td> 9,2</td><td> 0,97</td><td> 0</td><td> 0,0</td>

<td> 48</td><td> 1</td><td> 285</td><td> 0</td><td> 63</td><td> 37,6</td><td> 9,7</td><td> 1</td><td> 2</td><td> 0,0</td>

<td> 47</td><td> 1</td><td> 285</td><td> 1</td><td> 63</td><td> 40,4</td><td> 9,95</td><td> 0,98</td><td> 123,4</td><td> 1,3</td>

<td> 76</td><td> 1</td><td> 285</td><td> 1</td><td> 63</td><td> 37,8</td><td> 9,9</td><td> 1,02</td><td> 99,4</td><td> 1,1</td>

<td> 51</td><td> 5</td><td> 275</td><td> 0</td><td> 129</td><td> 35,3</td><td> 44,8</td><td> 4,93</td><td> 2</td><td> 0,0</td>

<td> 56</td><td> 5</td><td> 285</td><td> 0</td><td> 29</td><td> 37,7</td><td> 45,7</td><td> 4,71</td><td> 2</td><td> 0,0</td>

<td> 77</td><td> 5</td><td> 285</td><td> 1</td><td> 29</td><td> 36,8</td><td> 42,85</td><td> 4,53</td><td> 299,4</td><td> 1,3</td>

<td> 6</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 7</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 8</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 31</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 32</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 33</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 60</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 61</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td> 64</td><td></td><td> 280</td><td></td><td> 100</td><td></td><td></td><td></td><td></td><td></td>

<td>Sample</td><td>ICP Al (PPm)</td><td>ICP Li (PPm)</td><td>ICPP (PPm)</td><td>Temp. (° C)</td><td>XRFSb (PP®)</td><td>XRFP (PP®)</td><td>IhV (dL / g)</td><td>ItV (dL / g)</td>

<td> 21</td><td> 9,2</td><td> 2,4</td><td> 0</td><td> 275</td><td></td><td></td><td> 0,784</td><td> 0,828</td>

<td> 71</td><td> 10,6</td><td> 2,5</td><td> 21,1</td><td> 275</td><td></td><td></td><td> 0,775</td><td> 0,818</td>

<td> 10</td><td> 9,6</td><td> 2,5</td><td> 3,4</td><td> 285</td><td></td><td></td><td> 0,86</td><td> 0,914</td>

<td> 39</td><td> 10,8</td><td> 2,5</td><td> 12,9</td><td> 285</td><td></td><td></td><td> 0,823</td><td> 0,872</td>

<td> 49</td><td> 9</td><td> 8</td><td> 26,7</td><td> 280</td><td></td><td></td><td> 0,895</td><td> 0,953</td>

<td> 50</td><td> 10,9</td><td> 11,4</td><td> 2</td><td> 275</td><td></td><td></td><td> 0,876</td><td> 0,932</td>

<td> 72</td><td> 13,4</td><td> 11,9</td><td> 55,4</td><td> 275</td><td></td><td></td><td> 0,781</td><td> 0,825</td>

<td> 25</td><td> 11,4</td><td> 11,1</td><td> 1,9</td><td> 285</td><td></td><td></td><td> 0,87</td><td> 0,925</td>

<td> 67</td><td> 9,5</td><td> 11,1</td><td> 62,4</td><td> 285</td><td></td><td></td><td> 0,775</td><td> 0,818</td>

<td> 66</td><td> 26,3</td><td> 6</td><td> 29,8</td><td> 280</td><td></td><td></td><td> 0,843</td><td> 0,894</td>

<td> 26</td><td> 21,2</td><td> 17,2</td><td> 1,8</td><td> 280</td><td></td><td></td><td> 0,889</td><td> 0,947</td>

<td> 1</td><td> 23,2</td><td> 19,3</td><td> 50,2</td><td> 280</td><td></td><td></td><td> 0,869</td><td> 0,924.</td>

<td> 2</td><td> 24,6</td><td> 19,6</td><td> 61,6</td><td> 280</td><td></td><td></td><td> 0,824</td><td> 0,873</td>

<td> 3</td><td> 24,8</td><td> 19,5</td><td> 59,5</td><td> 280</td><td></td><td></td><td> 0,83</td><td> 0,88</td>

<td> 27</td><td> 24,7</td><td> 18,5</td><td> 46,3</td><td> 280</td><td></td><td></td><td> 0,813</td><td> 0,861</td>

<td> 28</td><td> 22</td><td> 17,7</td><td> 44,7</td><td> 280</td><td></td><td></td><td> 0,813</td><td> 0,861</td>

<td> 29</td><td> 22,8</td><td> 18,3</td><td> 55,3</td><td> 280</td><td></td><td></td><td> 0,82</td><td> 0,868</td>

<td> 57</td><td> 23</td><td> 18,3</td><td> 43,7</td><td> 280</td><td></td><td></td><td> 0,812</td><td> 0,859</td>

<td> 58</td><td> 22,8</td><td> 18,9</td><td> 51,3</td><td> 280</td><td></td><td></td><td> 0,841</td><td> 0,892</td>

<td> 59</td><td> 24,5</td><td> 18,5</td><td> 54,4</td><td> 280</td><td></td><td></td><td> 0,818</td><td> 0,555</td>

<td> 73</td><td> 24</td><td> 18,6</td><td> 47,6</td><td> 285</td><td></td><td></td><td> 0,822</td><td> 0,871</td>

<td> 69</td><td> 25</td><td> 28,4</td><td> 85,4</td><td> 280</td><td></td><td></td><td> 0,773</td><td> 0,816</td>

<td> 20</td><td> 36,7</td><td> 9,2</td><td> 0</td><td> 275</td><td></td><td></td><td> 0,855</td><td> 0,908</td>

<td> 48</td><td> 37,6</td><td> 9,7</td><td> 2</td><td> 285</td><td></td><td></td><td> 0,835</td><td> 0,885</td>

<td> 47</td><td> 40,4</td><td> 9,95</td><td> 123,4</td><td> 285</td><td></td><td></td><td> 0,714</td><td> 0,75</td>

<td> 76</td><td> 37,8</td><td> 9,9</td><td> 99,4</td><td> 285</td><td></td><td></td><td> 0,723</td><td> 0,76</td>

<td> 51</td><td> 35,3</td><td> 44,8</td><td> 2</td><td> 275</td><td></td><td></td><td> 0,89</td><td> 0,948</td>

<td> 56</td><td> 37,7</td><td> 45,7</td><td> 2</td><td> 285</td><td></td><td></td><td> 0,804</td><td> 0,85</td>

<td> 77</td><td> 36,8</td><td> 42,85</td><td> 299,4</td><td> 285</td><td></td><td></td><td> 0,658</td><td> 0,688</td>

<td> 6</td><td></td><td></td><td></td><td> 280</td><td> 238,6</td><td> 74,5</td><td> 0,728</td><td> 0,766</td>

<td> 7</td><td></td><td></td><td></td><td> 280</td><td> 242,1</td><td> 72,1</td><td> 0,746</td><td> 0,786</td>

<td> 8</td><td></td><td></td><td></td><td> 280</td><td> 226,4</td><td> 65,8</td><td> 0,763</td><td> 0,804</td>

<td> 31</td><td></td><td></td><td></td><td> 280</td><td> 229,8</td><td> 92,8</td><td> 0,708</td><td> 0,743</td>

<td> 32</td><td></td><td></td><td></td><td> 280</td><td> 238</td><td> 57,2</td><td> 0,769</td><td> 0,811</td>

<td> 33</td><td></td><td></td><td></td><td> 280</td><td> 234,9</td><td> 65,3</td><td> 0,764</td><td> 0,806</td>

<td> 60</td><td></td><td></td><td></td><td> 280</td><td> 241,8</td><td> 110,4</td><td> 0,758</td><td> 0,799</td>

<td> 61</td><td></td><td></td><td></td><td> 280</td><td> 245,9</td><td> 119,2</td><td> 0,792</td><td> 0,837</td>

<td> 64</td><td></td><td></td><td></td><td> 280</td><td> 245,3</td><td> 104,2</td><td> 0,776</td><td> 0,819</td>

<td>Sample</td><td>ICP Al (PPm)</td><td>Relationship Molar Li: Al</td><td>ICP Li (PPm)</td><td>Temp. (° C)</td><td>Relationship Molar Q: M</td><td>ICPP (PPm)</td><td>Crist%</td>

<td> 21</td><td> 9,2</td><td> 1</td><td> 2,4</td><td> 275</td><td> 0</td><td> 0</td><td> 39,6</td>

<td> 71</td><td> 10,6</td><td> 1</td><td> 2,5</td><td> 275</td><td> 1</td><td> 21,1</td><td> 37,1</td>

<td> 10</td><td> 9,6</td><td> 1</td><td> 2,5</td><td> 285</td><td> 0</td><td> 3,4</td><td> 34,4</td>

<td> 39</td><td> 10,8</td><td> 1</td><td> 2,5</td><td> 285</td><td> 1</td><td> 12,9</td><td> 34,6</td>

<td> 49</td><td> 9</td><td> 3</td><td> 8</td><td> 280</td><td> 0,5</td><td> 26,7</td><td> 34,3</td>

<td> 50</td><td> 10,9</td><td> 5</td><td> 11,4</td><td> 275</td><td> 0</td><td> 2</td><td> 32,7</td>

<td> 72</td><td> 13,4</td><td> 5</td><td> 11,9</td><td> 275</td><td> 1</td><td> 55,4</td><td> 33,9</td>

<td> 25</td><td> 11,4</td><td> 5</td><td> 11,1</td><td> 285</td><td> 0</td><td> 1,9</td><td> 39,3</td>

<td> 67</td><td> 9,5</td><td> 5</td><td>n, i</td><td> 285</td><td> 1</td><td> 62,4</td><td> 38,9</td>

<td> 66</td><td> 26,3</td><td> 1</td><td> 6</td><td> 280</td><td> 0,5</td><td> 29,8</td><td> 36,5</td>

<td> 26</td><td> 21,2</td><td> 3</td><td> 17,2</td><td> 280</td><td> 0</td><td> 1,8</td><td> 50,4</td>

<td> 1</td><td> 23,2</td><td> 3</td><td> 19,3</td><td> 280</td><td> 0,5</td><td> 50,2</td><td> 38</td>

<td> 2</td><td> 24,6</td><td> 3</td><td> 19,6</td><td> 280</td><td> 0,5</td><td> 61,6</td><td> 35,2</td>

<td> 3</td><td> 24,8</td><td> 3 </td><td> 19,5</td><td> 280</td><td> 0,5</td><td> 59,5</td><td> 35,1</td>

<td> 27</td><td> 24,7</td><td> 3</td><td> 18,5</td><td> 280</td><td> 0,5</td><td> 46,3</td><td> 40,4</td>

<td> 28</td><td> 22</td><td> 3</td><td> 17,7</td><td> 280</td><td> 0,5</td><td> 44,7</td><td> 41,9</td>

<td> 29</td><td> 22,8</td><td> 3</td><td> 18,3</td><td> 280</td><td> 0,5</td><td> 55,3</td><td> 32,6</td>

<td> 57</td><td> 23</td><td> 3</td><td> 18,3</td><td> 280</td><td> 0,5</td><td> 43,7</td><td> 30,9</td>

<td> 58</td><td> 22,8</td><td> 3</td><td> 18,9</td><td> 280</td><td> 0,5</td><td> 51,3</td><td> 41,9</td>

<td> 59</td><td> 24,5</td><td> 3</td><td> 18,5</td><td> 280</td><td> 0,5</td><td> 54,4</td><td> 40,3</td>

<td> 73</td><td> 24</td><td> 3</td><td> 18,6</td><td> 285</td><td> 0,5</td><td> 47,6</td><td> 36,3</td>

<td> 69</td><td> 25</td><td> 5</td><td> 28,4</td><td> 280</td><td> 0,5</td><td> 85,4</td><td> 37,1</td>

<td> 20</td><td> 36,7</td><td> 1</td><td> 9,2</td><td> 275</td><td> 0</td><td> 0</td><td> 30,8</td>

<td> 48</td><td> 37,6</td><td> 1</td><td> 9,7</td><td> 285</td><td> 0</td><td> 2</td><td> 36,4</td>

<td> 47</td><td> 40,4</td><td> 1</td><td> 9,95</td><td> 285</td><td> 1</td><td> 123,4</td><td> 39,4</td>

<td> 76</td><td> 37,8</td><td> 1</td><td> 9,9</td><td> 285</td><td> 1</td><td> 99,4</td><td> 49,2</td>

<td> 51</td><td> 35,3</td><td> 5</td><td> 44,8</td><td> 275</td><td> 0</td><td> 2</td><td> 38,8</td>

<td> 56</td><td> 37,7</td><td> 5</td><td> 45,7</td><td> 285</td><td> 0</td><td> 2</td><td> 39,2</td>

<td> 77</td><td> 36,8</td><td> 5</td><td> 42,85</td><td> 285</td><td> 1</td><td> 299,4</td><td> 36,8</td>

<td> 6</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 40,4</td>

<td> 7</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 38,3</td>

<td> 8</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 39,6</td>

<td> 31</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 37,3</td>

<td> 32</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 38.2</td>

<td> 33</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 37,3</td>

<td> 60</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 39,6</td>

<td> 61</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 41,3</td>

<td> 64</td><td></td><td></td><td></td><td> 280</td><td></td><td></td><td> 37,2</td>

<td>Sample</td><td>ICP Al (PPm)</td><td>ICP Li (PPm)</td><td>ICPP (PPm)</td><td>Temp. (° C)</td><td>AA Residual (PPm)</td><td>GEN. AA 295/5 (PPm)</td><td>Ger. AA 275/10 (ppm)</td><td>VEG (small / g)</td>

<td> 21</td><td> 9,2</td><td> 2,4</td><td> 0</td><td> 275</td><td> 21,0</td><td> 18,5</td><td> 15,4</td><td> 0,5</td>

<td> 71</td><td> 10,6</td><td> 2,5</td><td> 21,1</td><td> 275</td><td> 11,8</td><td> 9,4</td><td> 7,3</td><td> 1,4</td>

<td> 10</td><td> 9,6</td><td> 2,5</td><td> 3,4</td><td> 285</td><td> 37,7</td><td> 22,7</td><td> 22,9</td><td> 1,4</td>

<td> 39</td><td> 10,8</td><td> 2,5</td><td> 12,9</td><td> 285</td><td> 18,1</td><td> 12,7</td><td> 10,5</td><td> 2,9</td>

<td> 49</td><td> 9</td><td> 8</td><td> 26,7</td><td> 280</td><td> 17,6</td><td> 8,7</td><td> 6,0</td><td> 0,7</td>

<td> 50</td><td> 10,9</td><td> 11,4</td><td> 2</td><td> 275</td><td> 25,6</td><td> 22,1</td><td> 16,9</td><td> 0,2</td>

<td> 72</td><td> 13,4</td><td> 11,9</td><td> 55,4</td><td> 275</td><td> 11,0</td><td> 10,0</td><td> 6,6</td><td> 0,7</td>

<td> 25</td><td> 11,4</td><td>n, i</td><td> 1,9</td><td> 285</td><td> 38,0</td><td> 22,9</td><td> 20,0</td><td> 0,3</td>

<td> 67</td><td> 9,5</td><td> 11,1</td><td> 62,4</td><td> 285</td><td> 21,8</td><td> 12,7</td><td> 9,8</td><td> 1,4</td>

<td> 66</td><td> 26,3</td><td> 6</td><td> 29,8</td><td> 280</td><td> 17,0</td><td> 9,5</td><td> 6,0</td><td> 1,4</td>

<td> 26</td><td> 21,2</td><td> 17,2</td><td> 1,8</td><td> 280</td><td> 35,9</td><td> 25,6</td><td> 17,5</td><td> 0,2</td>

<td> 1</td><td> 23,2</td><td> 19,3</td><td> 50,2</td><td> 280</td><td> 4,9</td><td> 9,8</td><td> 6,7</td><td> 0,6</td>

<td> 2</td><td> 24,6</td><td> 19,6</td><td> 61,6</td><td> 280</td><td> 4,1</td><td> 8,1</td><td> 6,1</td><td> 0,9</td>

<td> 3</td><td> 24,8</td><td> 19,5</td><td> 59,5</td><td> 280</td><td> 4,1</td><td> 9,7</td><td> 5,7</td><td> 0,9</td>

<td> 27</td><td> 24,7</td><td> 18,5</td><td> 46,3</td><td> 280</td><td> 12,8</td><td> 9,7</td><td> 7,2</td><td> 0,4</td>

<td> 28</td><td> 22</td><td> 17,7</td><td> 44,7</td><td> 280</td><td> 15,1</td><td> 9,3</td><td> 7,4</td><td> 0,4</td>

<td> 29</td><td> 22,8</td><td> 18,3</td><td> 55,3</td><td> 280</td><td> 16,5</td><td> 9,0</td><td> 9,6</td><td> 0,4</td>

<td> 57</td><td> 23</td><td> 18,3</td><td> 43,7</td><td> 280</td><td> 15,4</td><td> 10,5</td><td> 8,2</td><td> 0,4</td>

<td> 58</td><td> 22,8</td><td> 18,9</td><td> 51,3</td><td> 280</td><td> 16,6</td><td> 8,7</td><td> 5,8</td><td> 0,8</td>

<td> 59</td><td> 24,5</td><td> 18,5</td><td> 54,4</td><td> 280</td><td> 12,8</td><td> 8,5</td><td> 7,9</td><td> 0,9</td>

<td> 73</td><td> 24</td><td> 18,6</td><td> 47,6</td><td> 285</td><td> 22,9</td><td> 10,3</td><td> 7,3</td><td> 1</td>

<td> 69</td><td> 25</td><td> 28,4</td><td> 85,4</td><td> 280</td><td> 21,7</td><td> 9,4</td><td> 6,2</td><td> 0,7</td>

<td> 20</td><td> 36,7</td><td> 9,2</td><td> 0</td><td> 275</td><td> 24,0</td><td> 23,0</td><td> 18,9</td><td> 0,2</td>

<td> 48</td><td> 37,6</td><td> 9,7</td><td> 2</td><td> 285</td><td> 44,7</td><td> 27,6</td><td> 21,0</td><td> 0,2</td>

<td> 47</td><td> 40,4</td><td> 9,95</td><td> 123,4</td><td> 285</td><td> 35,5</td><td> 21,7</td><td> 20,6</td><td> 0,8</td>

<td> 76</td><td> 37,8</td><td> 9,9</td><td> 99,4</td><td> 285</td><td> 30,7</td><td> 17,5</td><td> 15,8</td><td> 1,1</td>

<td> 51</td><td> 35,3</td><td> 44,8</td><td> 2</td><td> 275</td><td> 26,2</td><td> 34,2</td><td> 22,6</td><td> 0,2</td>

<td> 56</td><td> 37,7</td><td> 45,7</td><td> 2</td><td> 285</td><td> 65,4</td><td> 41,0</td><td> 25,7</td><td> 0,2</td>

<td> 77</td><td> 36,8</td><td> 42,85</td><td> 299,4</td><td> 285</td><td> 41,6</td><td> 18,6</td><td> 13,8</td><td> 1,4</td>

<td> 6</td><td></td><td></td><td></td><td> 280</td><td> 22,9</td><td> 31,7</td><td></td><td> 0,9</td>

<td> 7</td><td></td><td></td><td></td><td> 280</td><td> 30,1</td><td> 33,4</td><td> 25,0</td><td> 1</td>

<td> 8</td><td></td><td></td><td></td><td> 280</td><td> 29,4</td><td> 33,3</td><td> 23,6</td><td> 1,1</td>

<td> 31</td><td></td><td></td><td></td><td> 280</td><td> 28,2</td><td> 28,2</td><td> 20,8</td><td> 1,2</td>

<td> 32</td><td></td><td></td><td></td><td> 280</td><td> 34,2</td><td> 34,1</td><td> 26,9</td><td> 0,7</td>

<td> 33</td><td></td><td></td><td></td><td> 280</td><td> 36,6</td><td> 34,9</td><td> 18,2</td><td> 0,5</td>

<td> 60</td><td></td><td></td><td></td><td> 280</td><td> 25,6</td><td> 31,0</td><td> 22,5</td><td> 1,2</td>

<td> 61</td><td></td><td></td><td></td><td> 280</td><td> 33,6</td><td> 33,7</td><td> 15,9</td><td> 1</td>

<td> 64</td><td></td><td></td><td></td><td> 280</td><td> 31,3</td><td> 34,4</td><td> 22,2</td><td> 1</td>

<td>Sample</td><td>AA Residual (ppm)</td><td>GER AA 295/5 (ppm)</td><td>Ger. AA 275/10 (ppm)</td>

<td>CB-12</td><td> 0,8</td><td> 17,6</td><td> 14,7</td>

<td>CB-12</td><td> 0,7</td><td> 16,9</td><td> 14,7</td>

<td>CB-12</td><td> 0,7</td><td> 16,0</td><td> 14,2</td>

<td>CB-12</td><td> 0,9</td><td> 18,2</td><td> 19,3</td>

<td>CB-12</td><td> 0,8</td><td> 16,5</td><td> 14,2</td>

<td>CB-12</td><td></td><td></td><td> 14,8</td>

<td>CB-12</td><td></td><td></td><td> 14,7</td>

<td>CB-12</td><td> 0,8</td><td> 17,3</td><td> 14,9</td>

<td>CB-12</td><td></td><td> 18,8</td><td> 16,0</td>

Eastman Chemical Company's commercial polyester available as CB-12 is subjected when the AA generation test is done on the experimental samples.

Samples 21, 10, 50, 25, 26, 20, 48, 51 and 56 have 5 no deactivators added later. Low levels of vinyl terminals (0.2 - 0.3 peq / g) are seen in all of these samples, except for -21 and -10. No deactivator means a catalyst that is active for both, for polycondensation and the conversion of vinyl end groups (VEG) to acetaldehyde (AA). Low levels of (VEG) in this situation indicates that the catalyst converted most of the VEG to AA. Without being limited by any theory, more VEGs are created and are available for conversion to AA as the polycondensation temperature rises under comparable circumstances. Again, without being limited by any theory, more catalyst, in the form of higher levels of aluminum and higher molar ratios Li: Al (MR) increases the conversion of VEG to AA. Sample 56 has an aluminum target of 40 ppm and a Li: Al MR of 5, and a polycondensation temperature of 285 ° C; for this reason, the generation of AA after melting at 295 ° C for 5 minutes in an extrusion plastometer is expected to be the highest ever seen for Li / Al catalyzed polymers. Sample 51 has an aluminum target of 40 ppm and a Li: Al MR of 5, and a polycondensation temperature of 275 ° C; for this reason, AA generation is expected to be the second highest ever for Li: / 1 catalyzed polymers. The next highest generation of AA is seen in Sample 48 when the condensing temperature is 285 ° C and the target for Al is 40 ppm but the Li: Al M is decreased to 1 (that is, the Li level drops from ~ 45 ppm to ~ 10 ppm).

The lowest generation rate of AA with no catalyst added is seen in Sample 21, which is the lowest polycondensation temperature (275 ° C), the lowest target for Al (10 ppm), and Li: Al MR ( 1) lower. VEGs are starting to accumulate (0.5 peq / g) due to low catalyst levels (9.2 ppm Al &amp; 2.4 ppm Li per ICP), and AA generation is declining as fewer VEGs are converted to AA. Presumably, the low catalytic activity for conversion from VEG to AA is supported by the low rate of polycondensation or time on the long finisher (274 min. Or ~ 4.5 hours). Sample 10 also has the lowest target for aluminum (10 ppm), and the lowest Li: Al MR (1); however, it has a higher temperature in polycondensation (285 ° C). More VEGs are manufactured at a higher temperature, and lower catalyst levels do not result in more conversion to AA; for this reason, VEG levels increase greatly (1.4 pph / g) only with slightly higher AA generation (22.7 ppm).

Samples 39 and 67 are examples of PET catalyzed with aluminum and lithium with the deactivator added later that has low levels of AA generation (&lt;15 ppm AA in the Ceast plastometer after 5 min at 295 ° C) and strong concentrations of terminal vinyl groups (&gt; 1 peq / g). Although the high temperature in the condensation and the smaller catalyst loads are similar to that of Sample 10, VEG is even higher in Sample 39 due to the presence of the deactivator, which still reduces the activity of the catalyst for converting VEG to AA and, consequently, the VEG accumulates more (2.9 peq / g). Sample 67 is similar to 39 in terms of Al level and polycondensation temperature; however, Li: Al MR is much higher. The additional Li shows results with a much shorter finisher time for the 67 as compared to 39. A much shorter finisher time results in a faster throughput rate and consequently more kilograms of polymer per unit time.

Samples 71 and 66 are examples of PET catalyzed with aluminum and lithium with the deactivator added later that has very low levels of AA generation (&lt;10 ppm AA in the Ceast plastometer after 5 min at 295 ° C) and strong concentrations of vinyl end groups (&gt; 1 peq / g). Although both samples have a Li: Al MR of 1, Sample 66 has a much shorter time on the finisher than 71, because it has —26 ppm Al instead of -10 ppm and a polycondensation temperature of 280 ° C instead of 275 ° C.

There were nine cycles performed with the identical targets: Al (-24 ppm), Li: Al molar ratio of 3 (~ 19ppm of Li), a polycondensation temperature of 280 ° C, and a molar ratio of phosphorus to metals (Li + Al) of 0.5. All nine cycles had a very low amount of AA generated (8.1 to 10.5 ppm) after processing in a plastometer for extrusion at 295 ° C for 5 minutes. Four of these cycles also had vinyl end groups (VEG) with or above 8 peq / g: Samples 2, 3, 58 &amp; 59. One cycle (Sample 1) had VEG of 6 peq / g. With the standard deviation of the VEG test being 0.11 peq / g at the 0.76 peq / g level, the 95% confidence interval around a single test is 0.8 ± 0.22 peq / g. With variability in the test, Sample 1 may have a VEG of 0.8 peq / g. Samples 27, 28, 29 &amp; 57 have VEG of 0.4 peq / g. There is also some variability in sample preparation. The combination of variability in Sample preparation and VEG testing can explain these low VEG numbers.

Samples 49, 72 and 69 are illustrations of PET catalyzed with aluminum and lithium with the deactivator added later that has very low levels of AA generation (10 ppm AA or less in the plastometer for extrusion Ceast after 5 minutes at 295 ° C) and vinyl end groups of 0.7 pq / g. With the variability of the test, these samples can have VEG of 0.8 peq / g or more.

Sample 77 is an illustration of PET catalyzed with aluminum and lithium with the deactivator added later that has a moderate level of AA generation (&gt; 15 ppm and &lt;22 ppm AA in the plastometer for extrusion Ceast after 5 minutes at 295 ° C) and strong concentrations of terminal vinyl groups (&gt; 1.0 peq / g). Manufactured with the same targets for catalyst and the same conditions, PET without deactivator (Sample 56) had a high generation of AA (41 ppm) and low VEG (0.2 peq / g). The addition of catalyst later decreased AA generation by about 55% and increased VEG 7-fold.

For the specific PET samples tested, there is an optimal P: M MR. In the laboratory where these samples were manufactured, the optimal P: M MR is between about 0.5 and 0.8, with the flatter area being generally between about 0.6 and 0.7. Since the P: M MR of 1 was used for Sample 77, the AA generation rate may still decrease if a P: M MR closer to the optimal level is used. AP: Optimal M MR may also depend on the method of adding interlayer catalyst. A sliding current approach, making the concentrate in situ, may have an optimal P: M MR greater than the more direct addition approach used here.

Comparative Example 2

A PET oligomer sample prepared from terephthalic acid and ethylene glycol, and also containing about 1.5 mole percent of about 35% cis / 65% trans 1,4-cyclohexanedimethanol was used in the polycondensation. The oligomer also contained about 1.2 percent diethylene glycol, which was generated during esterification. This oligomer has about 95% conversion of acid groups through titration / NMR of acid groups, an M_n around 766 g / moles, and one M_w 1478 g / moles.

Before being subjected to polycondensation, the ground oligomer (103 g) is weighed in a half-liter bottle, with a round bottom and a neck. The catalyst used is titanium tetrabutoxide and it is added to the flask. A stainless steel paddle stirrer and a glass polymer head were attached to the flask. After attaching the polymer head to a side arm and a purge hose, two nitrogen purges are completed.

The polymerization reactor is operated according to the CAMILE ™ automation system, programmed to implement the following arrangement.

<td>Internship</td><td>Time (minutes)</td><td>Temperature ° C</td><td>Vacuum (torr) (0.13 kPa)</td><td>Stirring Speed ​​(rpm)</td><td>Energy (kg-cm)</td><td>Flags</td>

<td> 1</td><td> 0,1</td><td> 270</td><td> 730</td><td> 0</td><td></td><td></td>

<td> 2</td><td> 10</td><td> 270</td><td> 730</td><td> 150*</td><td></td><td></td>

<td> 3</td><td> 2</td><td> 270</td><td> 140*</td><td> 300*</td><td></td><td></td>

<td> 4</td><td> 1</td><td> 270</td><td> 140</td><td> 300</td><td></td><td>Calibrate</td>

<td> 5</td><td> 10</td><td> 270</td><td> 25*</td><td> 300</td><td></td><td></td>

<td> 6</td><td> 10</td><td> 270</td><td> 25</td><td> 300</td><td></td><td></td>

<td> 7</td><td> 1</td><td> 270</td><td> 140*</td><td> 300</td><td></td><td></td>

<td> 8</td><td> 2</td><td> 270</td><td> 140</td><td> 300</td><td></td><td>Catalyst (P)</td>

<td> 9</td><td> 1</td><td> 270</td><td> 25*</td><td> 300</td><td></td><td></td>

<td> 10</td><td> 10</td><td> 270</td><td> 25</td><td> 300</td><td></td><td></td>

<td> 11</td><td> 2</td><td> 270</td><td> 2*</td><td> 30*</td><td></td><td></td>

<td> 12</td><td> 1</td><td> 270</td><td> 0,2*</td><td> 30</td><td></td><td>Vacuum</td>

<td> 13</td><td> 500#</td><td> 270</td><td> 0,2</td><td> 30</td><td>target</td><td>Energy</td>

* = ramp; # = termination with torque when the temperature = 300 ° C, change everything from 270 to 300 (the same for 285). when vacuum = 2 torr (0.3 kPa), change everything from 0.2 to 2 (the same for 1.1 torr (0.15 kPa)).

A Belmonte metal fusion bath is enlarged to surround the flask, and the CAMILE ™ arrangement is implemented. The temperature used for a given sample is that indicated in Table 3. In this arrangement, a “ramp” is defined as a linear change in vacuum, temperature, or stirring speed during the specified stage time. The stirring system is automatically calibrated between stages 4 and 5. After stage 6 ended, the vacuum level was raised to 140 torr (18.7 kPa), and then a 2 minute stage for adding phosphorus (stage 8) started.

A phosphorus compound, an oligomeric phosphate triester, is added only for the Sb controls. The finishing stage (13) is terminated when the agitator torque is such that it reaches the target (predetermined for a given temperature and polymer equipment) three times. Finisher stage time is referred to as “Time to reach IV”. Following the end of the laboratory arrangement or preparation, the polymer is cooled for about

15 minutes, separated from the glass vial, cooled for about 10 minutes and then immediately placed into liquid nitrogen. The polymer is cryogenically ground to pass through a 3 mm sieve.

The ground polymer is analyzed for acetaldehyde generation rate (AA generation), inherent viscosity and VEG. The data can be seen in Table 3. Ger. Average AA of the production of PET pellets, CB-12, tested at the same time was 25 ppm. (none of these are subjected to

Examples of the invention; all are Comparative Examples).

<td>Example</td><td>You Target ppm</td><td>Temp. degrees ° C</td><td>Vac. torr (0.13 kPa)</td><td>Time to reach IV (min.)</td><td>IhV dL / g</td><td>Groups Terminals Vinyls (small / g)</td><td>AA 295/5 Ger ppm</td>

<td>Control¹</td><td></td><td> 285</td><td> 1,1</td><td> 103,32</td><td> 0,805</td><td> 0,9</td><td> 29,35</td>

<td>Cl</td><td> 10</td><td> 285</td><td> 1,1</td><td> 45,38</td><td> 0,796</td><td> 0,2</td><td> 37,565</td>

<td>C2</td><td> 15</td><td> 270</td><td> 2</td><td> 158,97</td><td> 0,803</td><td> 0,1</td><td> 41,255</td>

<td>C3</td><td> 10</td><td> 285</td><td> 1,1</td><td> 57,12</td><td> 0,838</td><td> 0,1</td><td> 38,93</td>

<td>C4</td><td> 15</td><td> 300</td><td> 0,2</td><td> 9,47</td><td> 0,791</td><td> 0,6</td><td> 40,805</td>

<td>C5</td><td> 5</td><td> 270</td><td> 0,2</td><td> 123,64</td><td> 0,795</td><td> 1,2</td><td> 28,34</td>

<td>C6</td><td> 5</td><td> 300</td><td> 2</td><td> 54,77</td><td> 0,831</td><td> 5,4</td><td> 38,52</td>

<td>C7</td><td> 10</td><td> 285</td><td> 1,1</td><td> 56,5</td><td> 0,829</td><td> 0,2</td><td> 39,93</td>

<td>Control</td><td></td><td> 285</td><td> 1,1</td><td> 91,46</td><td> 0,771</td><td> 0,7</td><td> 34,405</td>

<td>Control</td><td></td><td> 285</td><td> 1,1</td><td> 93,04</td><td> 0,789</td><td> 0,9</td><td> 30,97</td>

<td>C8</td><td> 5</td><td> 270</td><td> 2</td><td> 223,17</td><td> 0,781</td><td> 0,7</td><td> 23,96</td>

<td>C9</td><td> 5</td><td> 300</td><td> 0,2</td><td> 30,08</td><td> 0,805</td><td> 4,2</td><td> 38,465</td>

<td>CIO</td><td> 15</td><td> 270</td><td> 0,2</td><td> 51,43</td><td> 0,766</td><td> 0</td><td> 40,72</td>

<td>Cll</td><td> 15</td><td> 300</td><td> 2</td><td> 16,22</td><td> 0,771</td><td> 0,4</td><td> 46,15</td>

<td> 02</td><td> 10</td><td> 285</td><td> 1,1</td><td> 49,39</td><td> 0,834</td><td> 0,4</td><td> 28,13</td>

<td>Control</td><td></td><td> 285</td><td> 1,1</td><td> 106,01</td><td> 0,807</td><td> 0,8</td><td> 32,415</td>

<td> 03</td><td> 10</td><td> 285</td><td> 1,1</td><td> 43,4</td><td> 0,792</td><td> 0,3</td><td> 38,005</td>

<td> 04</td><td> 10</td><td> 285</td><td></td><td> 51,92</td><td> 0,852</td><td> 0,8</td><td> 28,21</td>

* Controls had targets of 220 ppm Sb &amp; 17 ppm P.

In Table 3, all PET's with a Ti catalyst and without 15 deactivator added later have AA generation rates of more than 22 ppm when melting at 295 ° C for 5 minutes in an extrusion plastometer. The two samples (C6 &amp; C9) with the strongest VEG have a low level of Ti and a high temperature in polycondensation. The higher temperature (300 ° C) results in more thermal degradation of PET, and consequently, more VEG than can be converted to AA with a low level of TI (5 ppm). When the Ti level is higher at high temperature (C4 &amp; Cl 1), the VEG level drops, and the AA generation increases. Example 2

To manufacture the phosphorous acid salts of Cyasorb UV 3529, two moles of phosphorous acid were used per mole of Cyasorb UV 3529, and reacted according to the following procedure. The salts can be manufactured according to the description in the co-pending US order No. Series 10 / 392,575, which is fully incorporated here by reference.

411.76 g of Cyasorb UV-3529 and 945 g of toluene are added to a 5 1 round-bottom flask equipped with a mechanical stirrer, thermocouple and a heating mantle. Cyasorb UV-3529 is a polymeric hindered amine light stabilizer that conforms as believed, generally to the compounds of the amine formula (12) previously specified, where R &lt;, = R₇ = Rg = R₉ = Rio = methyl; Li is hexamethylene; e (R₃) and (R4) N- collectively represent a morpholino group (see also formula 21). The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. Isopropyl alcohol (370 g) is added to the reaction vessel. A solution of 115.46 g (1.41 moles) of phosphorous acid dissolved in 370 g of isopropyl alcohol is added in a constant small stream (in rapid drops) via an additional funnel to the Cyasorb UV-3529 solution with stirring for approximately 30 minutes. A homogeneous solution is obtained and stirred for 15 minutes once the addition is complete.

The reaction mixture was pumped with about 5 ml / min into a 12 1 reaction vessel that contained about 7 l of rapidly stirred heptane (4768 g) over a period of approximately 50 minutes. The rate of feeding the reaction mixture into the vessel containing heptane has some effect on the particle size of the final product.

Slow feeds tend to produce a fine powder while higher feed rates will result in a larger particle that appears to be almost agglomerated. This needs to be balanced by the tendency of the salt to stick to the flooded vessel if the feeding rate is too fast. After the addition was completed, the resulting slurry was stirred for about 60 minutes. The precipitate was collected by suction filtration. The filter cake was washed twice with 137 g of heptane and then dried by absorption on the filter paper overnight. The solid was placed in a metal container and dried overnight in a vacuum oven at 50 ° C with a light inflow of dry nitrogen. The dry product weighed approximately 531.8 g (101% of theory). The typical apparent density of the dry salt had been between 0.4 and 0.6 g / ml.

To test the phosphorous acid salts of Cyasorb UV-3529, melt mixing in a glass bottle achieves a uniform additive distribution within the polymer approximately simulating the mixing of an additive near the end of or after the reactor for final polycondensation.

This example used 100 g of modified PET with about 2.6 moles% isophthalic acid and about 4.2 moles% diethylene glycol. This PET was produced on a production scale line with 10 ppm Ti and 0 ppm P. The granules were ground to pass through a 2 mm sieve. Examples preceded by the letter “C” are comparative examples.

Polyester powders are weighed in 500 ml round bottom flasks. The powders are dried at 120 ° C under maximum vacuum overnight (about 16 hours) in a vacuum oven. After cooling the bottle to room temperature in a desiccator (about 1.5 hours), the additive is weighed into the bottle. The additive was marked to the level of 0.1% by weight. The mixing parameters are specified in the following table.

To mix the amine salts with the polymers, a polymer head with a stirrer is attached and the flask purged twice with nitrogen. The CAMILE ™ automation system is programmed for the next layout, as specified in the following table.

<td>Internship</td><td>Time min.</td><td>Temp. ° C</td><td>Vacuum Torr (0.13 kPa)</td><td>Agitation RPM</td><td>Energy Kg-cm</td><td>Estimated Final Time</td>

<td> 1</td><td> 1</td><td> 270</td><td> 730</td><td> 0</td><td> 0</td><td> 10:23:59</td>

<td> 2</td><td> 5</td><td> 270</td><td> 730</td><td> 0</td><td> 0</td><td> 10:28:59</td>

<td> 3</td><td> 5</td><td> 270</td><td> 730</td><td> 0</td><td> 0</td><td> 10:33:59</td>

<td> 4</td><td> 5</td><td> 270</td><td> 730</td><td> 15*</td><td> 0</td><td> 10:38:59</td>

<td> 5</td><td> 4</td><td> 270</td><td> 730</td><td> 35*</td><td> 0</td><td> 10:42:59</td>

<td> 6</td><td> 2</td><td> 270</td><td> 730</td><td> 75*</td><td> 0</td><td> 10:44:59</td>

<td> 7</td><td> 5</td><td> 270</td><td> 730</td><td> 75</td><td> 0</td><td> 10:49:59</td>

* = ramp

A moderate nitrogen purge was employed at all times. During stages 2 and 3, the mixer is turned off slowly manually. Following the end of the arrangement, the polymer is cooled, chopped, and ground to pass through a 3 mm sieve. The ground polymer is analyzed for acetaldehyde generation rate, concentration of vinyl end groups, and inherent viscosity. The results are shown in Table 4, where the fifth column from the left is the amount of additive added in grams, where the additive is the phosphorous acid salts of Cyasorb UV 3529.

Table 4

<td>Example</td><td>Additive</td><td>You (PPm)</td><td>P (PPm)</td><td>Additive Added (g)</td><td>IV (dL / g)</td><td>GEN. AA 295/5 (PPm)</td><td>% of Ger. Reduction from AA</td><td>VEG small / g</td>

<td> 05</td><td>none</td><td> 10</td><td> 0</td><td> 0</td><td> 0,797</td><td> 36,285</td><td> -1,7</td><td></td>

<td> 06</td><td>none</td><td> 13</td><td> 5</td><td> 0</td><td> 0,752</td><td> 33,94</td><td> 4,9</td><td> 0,4</td>

<td> 07</td><td>none</td><td> 10</td><td> 2</td><td> 0</td><td> 0,842</td><td> 36,82</td><td> -3,2</td><td> 0,5</td>

<td> 15</td><td>Cyasorb UV 3529- H3PO3</td><td> 12</td><td> 54</td><td> 0,106</td><td> 0,734</td><td> 9,325</td><td> 73,9</td><td> 1</td>

<td> 16</td><td>Cyasorb UV 3529- H3PO3</td><td> 10</td><td> 56</td><td> 0,1</td><td> 0,77</td><td> 8,465</td><td> 76,3</td><td> 1</td>

The% reduction in AA generation after melt processing in a plastometer for extrusion at 295 ° C for 5 minutes (GER. Of AA 295/5) was calculated as follows: 1) an average of Ger. AA for cycles without any additive was calculated to be 35.68 ppm, 2) to Ger. AA for a given cycle was divided by 35.68 ppm, 3) the quotient was multiplied by 100, and 4) the product was subtracted from 100. As can be seen from Table 5, the% reduction in Ger. AA 295/5 was around 75% to about 55 ppm P of phosphorous acid salts of Cyasorb UV 3529 (“Cyasorb UV 3529-H3PO3”). The average of Ger. of AA from the production of the CB-12 PET granules tested at the same time was 23.5 ppm, much higher than the 8.5 - 9.3 ppm in the examples of this invention. The VEG level of the PET after mixing in fusion with the phosphorous acid salts of Cyasorb UV 3529 is about double that without any deactivator present. The additive has at least partially deactivated the catalyst so that VEG has accumulated and less AA is generated since less VEG are converted to AA, as this conversion is largely catalyzed. On average, the inherent viscosities dropped moderately (&lt;0.05 dL / g) in the tested additive levels.

Samples 15 &amp; 16 are titanium-catalyzed PET, with the deactivator added later, which has AA generation rates much lower than 22 ppm when melting at 295 ° C for 5 minutes in an extrusion plastometer, and levels of terminal vinyl groups above 0.8 peq / g.

Example 3

This example uses the melt mixing procedure, starting polymer, product work and the phosphorous acid salt of Cyasorb UV 3529 described in Example 2. In addition, after cryogenically grinding the polyesters, residual AA samples are kept frozen until that are tested.

A series of polymers were prepared, employing various levels of Cyasorb UV 3529 phosphorous acid salt. The results are shown in Table 5, where the fifth column from the left is the inherent viscosity (IhV) in dL / g.

Table 5

<td>Sample</td><td>Cyasorb UV 3529H3PO3 Amt g</td><td>You (ppm)</td><td>P (PPm)</td><td>IhV dL / g</td><td>AA Residual PPm</td><td>% Reduced fromAA Residual</td><td>GEN. fromAA (PPm)</td><td>% of Ger. Reduction fromAA</td><td>VEG geq / g</td>

<td> 17</td><td> 0</td><td> 10</td><td> 1</td><td> 0,744</td><td> 17,21</td><td> 0,00</td><td> 35,32</td><td> 0,00</td><td> 0,3</td>

<td> 18</td><td> 0,02</td><td> 10</td><td> 16</td><td> 0,716</td><td> 4,45</td><td> 74,14</td><td> 10,07</td><td> 71,49</td><td> 0,8</td>

<td> 19</td><td> 0,04</td><td> 10</td><td> 29</td><td> 0,723</td><td> 9,07</td><td> 53,11</td><td> 9,27</td><td> 73,75</td><td> 1</td>

<td> 20</td><td> 0,06</td><td> 10</td><td> 39</td><td> 0,72</td><td> 6,11</td><td> 64,50</td><td> 10,28</td><td> 70,89</td><td> 1,1</td>

<td> 21</td><td> 0,08</td><td> 10</td><td> 46</td><td> 0,714</td><td> 4,14</td><td> 75,94</td><td> 7,4</td><td> 79,05</td><td> 0,8</td>

<td> 22</td><td> 0,1</td><td> 10</td><td> 61</td><td> 0,887</td><td> 4,32</td><td> 74,90</td><td> 7,61</td><td> 78,45</td><td> 0,9</td>

Table 5 indicates that even with a very low additive concentration, target for additive of 0.02 weight percent, or 16 ppm P, the phosphorous acid salts of Cyasorb UV 3529 provide a reduction (&gt; 70% reduction relative to no additives) of both, residual acetaldehyde as well as acetaldehyde generated when melting. Even with a very low concentration of additive, the concentration of VEG more than doubled compared to the case without additive.

Samples 18, 19, 20, 21 and 22 are titanium-catalyzed PET, with the deactivator added later, which has AA generation levels much lower than 22 ppm when melting at 295 ° C for 5 minutes in a plastometer for extrusion, and levels of vinyl end groups above 0.8 peq / g.

Example 4

To manufacture the phosphoric acid salts of Cyasorb UV 3529, two moles of phosphoric acid are used per mole of Cyasorb UV 3529, and reacted according to the following procedure.

41.18 g of Cyasorb UV-3529 and 94.51 g of toluene are added to a 500 ml round-bottom flask equipped with a magnetic stir bar, thermocouple and a heating mantle. Cyasorb UV3529 is a polymeric hindered amine light stabilizer that conforms as believed, generally for the compounds of the amine formula (12) previously specified, where R ^ = R₇ = R₈ = R₉ = R₁₀ = methyl; Li is hexamethylene; e (R₃) (R4) N- collectively represent a morpholino group (see also formula 21). The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. A solution of 16.23 g (0.141 moles) of phosphoric acid dissolved in 37.01 g of isopropyl alcohol is added in a constant small stream (in moderate drops) by adding a funnel to the Cyasorb UV-3529 solution with rapid stirring for approximately 100 minutes. If the addition is too fast, large pieces of solids form and make it difficult to stir. A paste with slightly colored solids is obtained and is stirred for 15 minutes once the addition is complete. The precipitate is a mixture of a fine white powder and sticky amber globules coated with the white powder and is collected by suction filtration. The filter cake is washed with 7 portions of 40 ml of heptane and then dried by absorption in the filter paper for 2 hours. The solid is placed in a metal container and dried over the weekend at 50 ° C with the light inflow of dry nitrogen. The dry product weighed approximately 36.48 g (66% of theory; fines in the filtrate were not isolated).

An additional series of polymers was prepared, using the phosphoric acid salt of CYASORB UV 3529 ("Cyasorb UV 3529-H3PO4"). This example uses the melt mixing procedure, the starting polymer and the product work described in Example 3. For Sample 23, the phosphorous acid salt of CYASORB UV 3529 is the one described in Example 2. The results are shown in Table 6, in which the sixth column from the left contains inherent viscosity (IhV), in dL / g.

Table 6

<td>Example</td><td>Additive</td><td>Additive</td><td>You</td><td>P</td><td>IhV</td><td>FNAA</td><td>GER AA</td><td>VEG</td>

<td></td><td></td><td>Amount (g)</td><td>(ppm)</td><td>(ppm)</td><td>(dl / g)</td><td>(ppm)</td><td>295/5 (PPm)</td><td>small / g</td>

<td> 23</td><td>Cyasorb UV 3529-H3PO3</td><td> 0,102</td><td> 10</td><td> 66</td><td> 0,741</td><td> 3,1</td><td> 7,8</td><td> 1</td>

<td> 24</td><td>Cyasorb UV 3529-H3PO4</td><td> 0,105</td><td> 10</td><td> 83</td><td> 0,725</td><td> 3,6</td><td> 7,19</td><td> 0,9</td>

<td> 25</td><td>Cyasorb UV 3529-H3PO4</td><td> 0,106</td><td> 10</td><td> 99</td><td> 0,732</td><td> 3,34</td><td> 7,69</td><td> 0,5</td>

The cycles with phosphoric acid ended up having a slightly higher phosphorus level. According to Table 5, the level study with the phosphorous acid salts of Cyasorb UV 3529 did not indicate a large level impact on AA performance. Table 6 indicates that the levels of residual AA in the powders and the generation of AA when melting were very similar for both, the phosphoric acid salts of Cyasorb UV 3529 and the phosphorous acid salts of Cyasorb UV 3529. The average AA generation of the production of the PET granules tested at the same time was 22.6 ppm.

Samples 23 &amp; 24 are titanium-catalyzed PET, with the deactivator added later, which has AA generation levels much lower than 22 ppm when melting at 295 ° C for 5 minutes in an extrusion plastometer, and levels of terminal vinyl groups above 0.8 peq / g. Sample 25 is titanium-catalyzed PET, with the deactivator added later, which has AA generation levels much lower than 22 ppm when melting at 295 ° C for 5 minutes in an extrusion plastometer, and terminal group levels vinyls above 0.8 peq / g. Since Sample 25 is a replica of Sample 24, the combination of variability in sample preparation and VEG testing may explain the low number of VEGs in Sample 25.

Example 5

Other additives were also used: the phosphorous acid salt of N-methylpiperidine (“NPM-H₃POWDER₃”), The ammonium phosphorous acid salt (“ Ammonia- H₃POWDER₃”), And the phosphoric acid salt of N-methylpiperidine (“ NPM-H₃POWDER₄”).

To produce the phosphorous acid salts of N-methylpiperidine, one mole of phosphorous acid is used per mole of N-methylpiperidine, and is reacted according to the following procedure.

For a 500 ml round-bottom flask, equipped with a magnetic stir bar, thermocouple, and a heating blanket, 7.0 g of 1-methyl-piperidine (0.0704 moles) and 94.5 g of toluene are added . The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. A solution of 5.8 g (0.0704 moles) of phosphorous acid dissolved in 37.0 g of isopropyl alcohol is added in a constant small stream (in rapid drops) through an addition funnel to the 1-methyl solution -piperidine with rapid stirring for approximately 55 minutes. The reaction mixture was pumped at about 5 ml / min over a period of approximately 40 minutes into a 21 l reaction vessel, equipped with a mechanical stirrer, which contained about 7 ml of rapidly stirred heptane (476.8 g). After the addition was completed, the resulting solution was stirred for about 50 minutes. Suction filtration was started and then stopped when the product was determined to be a yellow oil containing some fine white solids. The solvent was rotoevaporated using a vacuum pump and a 55 ° C water bath. The paper filter and the flask were rinsed with heptane. The solvent was removed on a rotary evaporator. The oil was dried overnight and then for about 5 hours at about 50 ° C with a slight inflow of dry nitrogen. The product weighed 7.5 g (12.75 in theory).

To manufacture the ammonia phosphorous acid salts, one mole of phosphorous acid is used per mole of ammonia, and reacted according to the following procedure.

For a 500 ml round-bottom flask, equipped with a magnetic stir bar, thermocouple, and a heating mantle, 8.5 g of 28 - 30% ammonium hydroxide and 94.5 g of toluene are added. The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. A solution of 5.8 g (0.0704 moles) of phosphorous acid dissolved in 37.1 g of isopropyl alcohol is added in a constant small stream (in rapid drops) through an addition funnel to the ammonium hydroxide solution with rapid stirring for approximately 25 minutes. The solution is stirred for 15 minutes once the addition is complete. The reaction mixture was pumped at about 5 ml / min over a period of approximately 35 minutes into a 21 l reaction vessel, equipped with a mechanical stirrer, which contained about 700 ml of rapidly stirred heptane (476.8 g). After the addition was completed, the resulting solution was stirred for about 60 minutes. The solvent is rotoevaporated using a vacuum pump and a 55 ° C water bath. White semisolids were visible after all the solvent was removed. The flask was rinsed with heptane, isopropyl alcohol and Millpore water. The solvents were removed on a rotary evaporator. The white solid is dried overnight at about 50 ° C with the light inflow of dry nitrogen. The product weighed 7.3 g.

To manufacture the N-methylpiperidine phosphoric acid salts, one mole of phosphoric acid is used per mole of N-methylpiperidine, and is reacted according to the following procedure.

For a 500 ml round-bottom flask, equipped with a magnetic stir bar, thermocouple, and a heating mantle, 7.0 g of 1-methyl-piperidine and 94.5 g of toluene are added. The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. A solution of 8.1 g (0.0704 moles) of 85% phosphoric acid dissolved in 37 g of isopropyl alcohol is added in a constant small stream (in rapid drops) through an addition phonil to the 1- methylpiperidine with rapid stirring for approximately 50 minutes. A yellow liquid with a white ring of solids is obtained and stirred for 15 minutes once the addition is complete. After scraping the solids stuck to the flask, the precipitate was collected by suction filtration. The filter cake was washed with approximately eight 40 ml portions of heptane and then dried by absorption in the filter paper for 3 hours. The solid is placed in a metal container and dried overnight and most of the following day at 50 ° C with a light inflow of dry nitrogen. The product weighed 12.1 g.

This example uses the melt mixing procedure, the starting polymer, and the product work described in Example 3.

Table 7

<td>Ex.</td><td>Additive</td><td>Quantity added to the bottle (g)</td><td>XRF You (ppm)</td><td>XRF P (PPm)</td><td>IhV (dL / g)</td><td>AA Residual (ppm)</td><td>% Residual AA Reduction</td><td>GEN. AA 295/5 (PPm)</td><td>% in Reduction of Ger. from AA</td><td>VEG small / g</td>

<td>C-18</td><td>none</td><td> 0</td><td> 9</td><td> 3</td><td> 0,804</td><td> 21,25</td><td> -9,8</td><td> 30,54</td><td> -2,2</td><td> 0,3</td>

<td>C-19</td><td>none</td><td> 0</td><td> 10</td><td> 5</td><td> 0,79</td><td> 17,45</td><td> 9,8</td><td> 29,25</td><td> 2,2</td><td> 0,6</td>

<td>C-20</td><td>Cyasorb 3529</td><td> 0,099</td><td> 10</td><td> 1</td><td> 0,817</td><td> 17,43</td><td> 9,9</td><td> 25,71</td><td> 14</td><td> 0,4</td>

<td> 26</td><td>Cyasorb UV 3529- H3PO3</td><td> 0,101</td><td> 10</td><td> 57</td><td> 0,747</td><td> 4,57</td><td> 76,4</td><td> 11,96</td><td> 60</td><td> 0,8</td>

<td> 27</td><td>Cyasorb UV 3529- H3PO3</td><td> 0,103</td><td> 10</td><td> 59</td><td> 0,757</td><td> 3,53</td><td> 81,8</td><td> 12,4</td><td> 58,5</td><td> 1</td>

<td> 28</td><td>NMP- H3PO3</td><td> 0,048</td><td> 10</td><td> 66</td><td> 0,768</td><td> 7,18</td><td> 62,9</td><td> 20,73</td><td> 30,7</td><td> 1.1</td>

<td> 29</td><td>NMP- H3PO3</td><td> 0,052</td><td> 9</td><td> 85</td><td> 0,754</td><td> 13,87</td><td> 28,3</td><td> 18,88</td><td> 36,8</td><td> 0,8</td>

<td> 30</td><td>NMP- H3PO4</td><td> 0,053</td><td> 10</td><td> 78</td><td> 0,748</td><td> 13,94</td><td> 28</td><td> 20,35</td><td> 31,9</td><td> 1,2</td>

<td> 31</td><td>Ammonia- H3PO3</td><td> 0,028</td><td> 10</td><td> 63</td><td> 0,754</td><td> 6,78</td><td> 65</td><td> 19,33</td><td> 35,3</td><td> 0,9</td>

Samples 26, 27, 28, 29, 30 and 31 are titanium-catalyzed PET, with the deactivator added later, which has an amount of AA generated of less than 22 ppm, as measured when melted at 295 ° C for 5 minutes in an extrusion plastometer, and levels of vinyl end groups greater than or equal to 0.8 peq / g.

The salts shown in Table 7, the ones with the simplest and smallest organic bases, had about half the reduction in AA generation than those with Cyasorb UV 3529-H3PO3 salt. The simplest salts are also much less expensive. Some applications and situations may require less reduction in AA generation than others, and the simplest salts would provide an economical solution in these cases. The average AA generation of the CB-12 PET granule production tested at the same time was 22 ppm.

In addition, the cycle was also carried out to investigate the use of an amine additive itself, and not its salts. The results are shown as Example C-20 in Table 7. Cyasorb UV 3529 did not significantly reduce residual AA; however, there was a slight reduction in AA generation (10 - 15%). Ger. AA is greater than 22 ppm and the VEG level is less than 0.8 peq / g. Amines alone are much less effective at lowering acetaldehyde than amine salts made with phosphorus-containing acid.

Although the amine portion of the salt can remove some AA as shown in Table 8, the predominant mechanism for the salts is thought to decrease residual AA and AA generation is catalyst deactivation, without being limited by theory.

Example 6

The choice of an amino acid as the organic base offers the possibility that the carboxylic acid group of the amino acid can react within the PET chain.

To produce the phosphoric acid salts of L-histidine, two moles of phosphoric acid are used per mole of L-histidine, and reacted according to the following procedure.

To a 500 ml round-bottom flask, equipped with a magnetic stir bar, thermocouple, and a heating blanket, 10.94 g of L-histidine and 143.97 g of Millipore water are added. The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. A solution of 16.397g of phosphoric acid dissolved in 37 g of Millipore water is added in a constant small stream (in rapid drops) through an addition funnel to the L-histidine solution with rapid stirring for approximately 35 minutes. The solution is stirred for about 35 minutes once the addition is complete. The clear solution was transferred to a bottle with a 500 ml round bottomed neck. The aqueous solvent was removed by cold drying. The liquid was frozen while being manually rotated in an acetone / dry ice bath. A lipophilizer was used for 3 days, 4 hours and 17 minutes. The white solid weighed 24.829 g (would have

24.722 g). Through XRF, the% weight / weight of P in the white solid was 17.17% (it would have 17.6%).

To produce the phosphoric acid salts of L-alanine, one mole of phosphoric acid is used per mole of L-alanine, and reacted according to the following procedure.

For a 500 ml round-bottom flask, equipped with a magnetic stir bar, thermocouple, and a heating blanket, 6.275 g of L-alanine and 94.5 g of Millipore water are added. The slurry is heated to 60 ° C and stirred until a homogeneous solution is obtained. A solution of 8,201 g of phosphoric acid dissolved in 37.01 g of Millipore water is added in a constant small stream (in rapid drops) through an addition funnel to the L-alanine solution with rapid stirring for approximately 17 minutes. The solution is stirred for at least 15 minutes once the addition is complete. The clear solution was transferred to a bottle with a 500 ml round bottomed neck. The aqueous solvent was removed by cold drying. The liquid was frozen while being manually rotated in an acetone / dry ice bath. A lipophilizer was used for 1 day, 19 hours and 15 minutes. The viscous, clear oil weighed 14.808 g (theory 13.17 g). Through XRL, the% weight / weight of P in the clear oil was 11.92% (theory 16.6%).

Another series of polymers was prepared, using the phosphoric acid salt of L-histidine, the phosphoric acid salt of Lalanine, both described above in this example, and the phosphoric acid salt of CYASORB UV 3529 (“Cyasorb UV 3529-H3PO4” ) described in Example 4. These examples use the melt mixing procedure, the starting polymer, and the product work described in Example 3.

Table 8

<td>Ex.</td><td>Additive</td><td>Quantity added to the bottle (g)</td><td>XRF You (ppm)</td><td>XRF P (PPm)</td><td>IhV (dL / g)</td><td>AA Resid. (PPm)</td><td>% de Red de AA Residual</td><td>GEN. fromAA 295/5 (PPm)</td><td>% in Reduction of Ger. from AA</td><td>VEG small / g</td>

<td>C21</td><td>none</td><td> 0</td><td> 9</td><td> 2</td><td> 0,781</td><td> 11,5</td><td> 0</td><td> 28,7</td><td> 0</td><td> 0,3</td>

<td> 32</td><td>Cyasorb UV 3529Η3ΡΟ4</td><td> 0,108</td><td> 9</td><td> 90</td><td> 0,745</td><td> 1,5</td><td> 86,8</td><td> 7,2</td><td> 74,8</td><td> 0,9</td>

<td> 33</td><td>Histidine- Η3ΡΟ4</td><td> 0,047*</td><td> 10</td><td> 63</td><td> 0,756</td><td> 1,9</td><td> 83,2</td><td> 10,0</td><td> 65,1</td><td> 0,8</td>

<td> 34</td><td>Alanine- H3PO4</td><td> 0,057*</td><td> 10</td><td> 64</td><td> 0,736</td><td> 2,5</td><td> 78,7</td><td> 9,7</td><td> 66,1</td><td> 1,1</td>

* = targets

Samples 32, 33 and 34 are titanium-catalyzed PET, with the deactivator added later, which has AA generation levels much lower than 22 ppm when melting at 295 ° C for 5 minutes in an extrusion plastometer, and levels of vinyl end groups above 0.8 peq / g.

Table 8 indicates that the two amino acid salts of phosphoric acid reduce residual AA by 79 - 83% and AA generation when melting by 65 - 66%. The CYASORB UV 3529 phosphoric acid salt reduces residual AA by about 87%, the generation of AA when melting by about 75%. Although the percentage of reduction in AA generation is about 10% lower for the amino acid salts (about 64 ppm of P) than for the Cyasorb UV 3529 salt (about 90 ppm of P), the amino acids are less expensive, copolymerizable (less expected extraction capacity), and water soluble (no VOC during salt preparation). The phosphoric acid salt of L-alanine is an oil, which can make it more economical to add than a solid salt of the type of phosphoric acid salt of Lhistidine.

Although the embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Instead, the words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the invention.

Comparative Example 3

The layout of the oligomer, catalyst, procedure and polymerization is described in Comparative Example 2, and the oligomeric phosphate triester, added only during the prepolymer stages for the Sb controls in Comparative Example 2, is now added for a cycle catalyzed with Ti. After stage 6 ended, the vacuum level was raised to 140 torr (18.7 kPa), and then a 2 minute phosphorus addition stage (stage 8) begins. Free or residual AA samples are handled as described in Example 3.

Table 9

<td>Sample</td><td>Temp. (degrees ° C)</td><td>Vacuum (torr) (0.13 kPa)</td><td>Target P/ You MR</td><td>XRF P (PPm)</td><td>Time for catch up IV (min)</td><td>IV dL / g</td><td>Groups terminals Vinyls small / g</td><td>AA Residual (PPm)</td><td>GEN. from AA 295/5 (ppm)</td>

<td>C22</td><td> 270</td><td> 0,2</td><td> 0</td><td> 1,9</td><td> 59,55</td><td> 0,749</td><td> 0,20</td><td> 9,98</td><td> 28,06</td>

<td>C23</td><td> 270</td><td> 0,2</td><td> 1,6</td><td> 9</td><td> 302,82</td><td> 0,769</td><td> 4,10</td><td> 7,76</td><td> 13,32</td>

When the deactivator is added earlier, that is before the finishing stage, the time on the finisher increases greatly compared to the time on the finisher with no deactivator being added. Although the

Sample C23 is titanium-catalyzed PET, which has AA generation levels of less than 22 ppm when melting at 295 ° C for 5 minutes in an extrusion plastometer, and vinyl end group levels greater than or equal to 0 , 8 ppl / g time of the very long finishing stage is negative.