Multiple feeds of catalyst metals to a polyester production process

THE REPUBLIC OF POLAND (12) TRANSLATION OF THE EUROPEAN PATENT (19) PL (11) PL / EP 2052007

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Patent Office of the Republic of Poland (96) Date and number of the European patent application: 07/09/2007 07796741.2 (97) The grant of the European patent was announced:

28/03/2018 European Patent Bulletin 2018/13

EP 2052007 B1 (13) T3 (51) Int. Cl.

C08G 63/78 (2006.01) (54) Title of the invention:

NUMEROUS STREAMS OF CATALYST METALS IN THE POLYESTER MANUFACTURING PROCESS (3 °) rv

Priority:

28.07.2006 US 834 081 P

03/07/2007 US 714942 (43) Application announced:

On April 29, 2009 in the European Patent Bulletin no. 2009/18 (45) The following was announced about the submission of the translation of the patent:

31.07.2018 News of the Patent Office 2018/07 (73) Authorized by the patent:

GRUPO PETROTEMEX, SA DE CV, San Pedro Garza Garcia, MX (72) Inventor (s):

£ 2 JASON CHRISTOPHER JENKINS, Kingsport, US

O (74) Agent:

thing, pat. Piotr Kaminski

ABOUT KAMIŃSKI AND PARTNERS

S.¹ KANCELARIA PATENTOWA SP. P.

Q_ iii ul. Gerbera 14/13

J 05-500 Piaseczno

ABOUT.

Caution:

Within nine months of the publication of the information on the grant of the European patent, any person may file an objection to the European Patent Office against the European patent granted. The objection must be made in the form of a written statement of reasons. It is considered filed only when the opposition fee has been paid (Art. 99 (1) of the Convention on the Grant of European Patents).

NUMEROUS STREAMS OF CATALYST METALS IN THE POLYESTER MANUFACTURING PROCESS

1. Field of the Invention

The present invention relates to methods of feeding catalyst systems to a melt process for the production of polyester polymers, and more particularly to methods of separating batch catalyst solutions introduced into the melt process to provide a target amount and ratio of catalytic metals.

2. Background of the invention

Conventional melt feed systems for the production of polyester polymers require a catalyst mixer and a single vessel system to supply the required melt process point. The point of addition to the melt process depends on the type of esterification, i.e. whether it is direct or transesterification, the type of catalyst used, and the required polymer characteristics and processing time required. The authors of this publication recently discovered that certain alkaline earth or alkali metal ("M") and aluminum catalyst systems can be kept in solution under ambient conditions using specific solvents, such as monohydric alcohol ether or polyhydric alcohol ether solvents, as described in more detail below. These catalytic systems are sparingly soluble in ethylene glycol and precipitate easily when standing under ambient conditions, especially when the molar ratio M: Al is close to 1: 1 and / or when the amount of Al in the solution exceeds 3000 ppm.

Catalyst solutions having M: Al molar ratios close to 1: 1 have been found to be preferred, minimizing yellow color formation in the polyester polymer and providing less haze (greater clarity) in the catalyst solution. The catalyst mixer and single melt feed system produce polyester polymers with the same M: Al ratio, 1: 1 or different. However, there may be a situation where different polymers are required to be produced on one production line. Depending on the nature of the polymer change required, it may be necessary to adjust the M: Al molar ratio appropriately for each type of polyester polymer. In such a case, it would be impractical to design the process to provide the catalyst with a constant ratio to the melt process. Changing the catalyst ratio in a single mixer / feed system is impractical because a stock of previously used catalyst remains in the mixer, which makes the process inelastic.

A plant often has multiple production lines. One line may be configured to produce one polyester polymer with a specific set of features, while a second, concurrent line may be configured to produce a polyester polymer with a different set of features, each line requiring a different M: Al catalyst ratio. Providing different catalyst mixers for each line increases installation costs.

It would be advantageous to design a catalyst feed system that does not require depletion of stock in the catalyst mixer and allows for quick adjustments of the catalyst ratio to provide faster conversion of production parameters to produce different polyester polymers on the same line or to make necessary catalyst changes in situations where when the polymer for some reason begins to deviate from the specification on the same line and / or to provide a more economical system with one mixer supplying multiple lines with different catalyst ratios depending on the requirements of the individual lines.

3. Summary of the invention

This document describes how metals are fed to one or more melt process lines to make polyester polymers, including:

A. providing a first feed stream wherein said first feed stream has a first molar ratio and comprises a mixture of a metal A and another metal B;

B. providing a second feed stream wherein the first feed stream comprises metals A and B and the second feed stream comprises metal A or B, but not both, and wherein metal A is lithium or aluminum, metal B is lithium or aluminum and the second feed stream comprises lithium, the A: B molar ratio in the first feed stream being from 0.5: 1 to 3: 1; and

C. feeding said first stream to one or more melt process lines at the addition point in each line, and feeding said second feed stream:

(i) to one or more melt process lines upstream or downstream of the point of addition of the first feed stream to the melt line.

4. Brief description of the figures

Fig. 1 is a process flow diagram using a catalyst mixer and a metal reservoir to supply one melt production line.

Fig. 2 is a flow chart of a process using a catalyst mixer supplying two melt production lines and a metal tank supplying one or both alloy production lines.

5. Detailed Description of the Invention

The present invention may be better understood by referring to the following detailed description of the invention.

It should also be noted that the singular terms used in the specifications and appended claims also apply to the plural, unless the context clearly dictates otherwise. For example, a reference to processing or manufacturing a "polymer", "preform", "article", "container" or "bottle" also includes the processing or production of multiple polymers, preforms, articles, containers, or bottles.

References to a composition or solution containing an ingredient or polymer, respectively, also refer to other ingredients or other polymers in addition to the said ingredient or polymer, respectively.

The terms "comprises", "consists of" or "has" mean that at least one said compound, element, component, particle, method step, etc. must be present in the composition, solution, article, or method, without excluding, however, the presence of other compounds. compounds, catalysts, materials, particles, method steps etc. even if such other compounds, materials, particles, method steps etc. perform the same function as listed, unless expressly excluded in the claims.

It should further be understood that the provision of one or more method steps does not exclude the presence of additional method steps before or after the specified combined steps, or the presence of intermediate method steps between these clearly stated steps. In addition, the listing of process steps is a convenient means of identifying discrete activities or steps, and unless otherwise specified, the process steps listed may be ranked in any order.

The range expression includes all integers and their fractions that fall within that range. Expressing the temperature or temperature range of a process, reaction mixture or alloy, either as applied to a melt or polymer or as applied to a polymer, means in all cases that the limitation conditions are met if the temperature used, the actual temperature of the melt or polymer, or both, correspond temperature or within the specified range. The term "composition" or "solution" means that each of the listed ingredients is present in the composition or solution, but it is not implied that any ingredient in the composition or solution is unbound or unreacted. The composition may be in solid or liquid form. The stated ingredients of the composition can be bound, unbound, reacted, unreacted and, unless otherwise specified, at any oxidation state. For example, when the presence of "aluminum" or "Al" or lithium or "Li" is mentioned, it means aluminum or lithium atoms, respectively, but not their oxidation state, morphological state, structural state or chemical state, irrespective of whether or not the element is added to the solution, polymer, or composition, unless such states are specifically stated.

As used herein, the term "metal" means a metal atom,

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however, it is not associated with a specific oxidation state or chemical state. The metals may be in any chemical state, e.g., salt, chelate, complex or element form, and may have any oxidation state unless their specific oxidation state is expressly stated. The term "element", however, means zero oxidation state.

A reported amount of metal (e.g., ppm) is based on the amount of metal present in the solution, polymer or article, and not on the amount of the compound or salt, unless specifically stated as the amount of compound or salt.

where

It.V. values mentioned herein are expressed in dl / g and calculated from the log viscosity measured at 25 ° C in 60% phenol and 40% 1,1,2,2-tetrachloroethane (by weight). The polymer samples are dissolved in the solvent at a concentration of 0.25 g / 50 ml. The viscosity of the polymer solutions is determined with a Viscotek Modified Differential Viscometer. For a description of the principle of a Differential Viscometer, see ASTM D 5225. The log viscosity is calculated from the measured solution viscosity. The following equations describe such solution viscosity measurements and the calculation of the Ih.V. value followed by the It.V. value. based on Ih.V .:

where ninh = log viscosity at 25 ° C at a polymer concentration of 0.5 g / 100 ml 60% phenol and 40% 1,1,2,2-tetrachloroethane (by weight)

In = natural logarithm ts = flow time of the sample through the capillary to = the flow time of the solvent only through the capillary

C = concentration of polymer in grams per 100 ml of solvent (0.50%)

The Intrinsic Viscosity is the limit at infinite dilution of the specific viscosity of the polymer. It is defined by the following equation: where ηint = intrinsic viscosity ηr = relative viscosity = ts / to ηsp = specific viscosity = ηr -1

The calibration of the device consists in testing the reference material three times and then applying the appropriate mathematical equations in order to obtain the "acceptable" values ​​of Ih.V. The three values ​​used for calibration should be within the range of 0.010; otherwise, correct errors and repeat the standard tests until three consecutive results fall outside this range.

Calibration factor = allowable Ih.V. reference material / mean of three determinations The uncorrected log viscosity (ηinh) of each sample is calculated by

Inint = Hm (q_S.p / C) = lim (In η_Γ) / Ο

C-&gt; 0 C-&gt; 0 Viscotek Model Y501 Relative Viscometer according to the following equation: n_inh = [In (P₂/ KPi)] / C where

P2 = pressure in the capillary P2

Pi = pressure in the capillary Pi In = natural logarithm K = viscosity constant obtained from the reference reading

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

Corrected Ih.V. based on calibration with standard reference materials is calculated as follows:

Corrected value of Ih.V. = calculated value of Ih.V. x calibration factor

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

nint = 0.5 [e ^{0.5 x co}y^goved Ł.V. value - 1] + (0.75 x corrected Ih.v. value) The reference publication for estimating the intrinsic viscosity (Billmeyer relationship) is J. Polymer Sci., 4, pp. 83-86 (1949).

Alternatively, the It.V. can be measured using the above solvents and concentrations, and using the Differential Viscometer per ASTM D 5225-98.

The weight of the alkaline earth metal or alkali metal can be measured or calculated when added to the alloy or by analytical techniques for detecting the amount in the final polymer or article. Suitable methods for detecting the presence of alkali metals or alkaline earth metals include inductively coupled plasma optical emission spectrometry (ICP-OES). The concentration of alkaline earth metal or alkali metal or aluminum or phosphorus or any other element or metal is reported as parts per million metal atoms based on the weight of the polymer.

This document describes how metals are fed to one or more melt process lines to make polyester polymers, including:

A. providing a first feed stream wherein said first feed stream has a first molar ratio and comprises a mixture of a metal A and another metal B;

B. providing a second feed stream wherein the first feed stream comprises metals A and B and the second feed stream comprises metal A or B, but not both, and wherein metal A is lithium or aluminum, metal B is lithium or aluminum and the second feed stream comprises lithium, the A: B molar ratio in the first feed stream being from 0.5: 1 to 3: 1; and

C. feeding said first stream to one or more melt process lines at the addition point in each line, and feeding said second feed stream:

(i) to one or more melt process lines upstream or downstream of the point of addition of the first feed stream to the melt line.

Any metals that, in combination or individually, can increase the rate of reaction or aid in the esterification or transesterification or melt polycondensation of polyester polymers may be used in the first feed stream. Typical metals of this type include: titanium, tin, antimony, manganese, cobalt, germanium, zinc, aluminum, and alkaline earth metals or alkali metals such as lithium, sodium, potassium, magnesium, calcium, and combinations thereof. The catalytic metals can be added to the esterification zone, the polycondensation zone or any point in between. Typical catalytic compounds added to the melt process include titanium alkoxides; tin (II) or (IV) esters; zinc, manganese or magnesium acetates or benzoates; antimony trioxide, aluminum carboxylates or aluminum alkoxides, and alkaline earth metal or alkali metal hydroxides.

As used herein, the term "melt process" means the process used to prepare a polyester polymer, starting with the reactants and ending with a solid polymer. The melt process line is a production line for the production of polyester polymers in the melt. Each production line can be divided into multiple polycondensation lines if necessary or equipped with multiple cutters for the production of polyester pellets.

There is no restriction on the particular method of making the polyester polymer. The process of the present invention may be applied to any method of producing polyester polymers by a melt process, preferably a continuous melt process. An illustrative process in the alloy is described below.

This process begins in the esterification zone. In the esterification zone, one or more dicarboxylic acids, preferably aromatic dicarboxylic acids, or ester-forming derivatives thereof, and one or more diols, such as ethylene glycol, may be mixed in a paste preparation tank, and the paste is then continuously fed to an esterification reactor operating at a temperature of about 200 ° C to 300 ° C and at a pressure higher than atmospheric pressure, of from about 1 psig to about 70 psig. The residence time of the reactants in the reactor is typically from about one to five hours. Typically, dicarboxylic acids are directly esterified with diols at elevated pressure and at a temperature from about 240 ° C to about 285 ° C. The esterification reaction is continued until an acid or ester conversion of at least 70% is achieved, and more usually an acid or ester conversion of at least 85% is achieved to produce the required oligomeric mixture (also called "monomeric mixture").

The resulting oligomeric mixture formed in the esterification zone (including direct esterification and transesterification processes) contains BHET (bis (2-hydroxyethyl) terephthalate) monomer, low molecular weight oligomers, DEG and trace amounts of water, as this condensation by-product is not completely removed in the zone esterification, along with other trace impurities from raw materials and / or potentially from catalyzed side reactions, and other optionally added compounds such as toners and stabilizers. The relative amounts of BHET monomer and oligomeric compounds vary depending on whether a direct esterification process is used in which the amounts of oligomeric compounds are significant or even a majority, or a transesterification process in which the relative amount of BHET monomer outweighs the amount of oligomeric compounds . Water is removed as the esterification reaction proceeds to shift the equilibrium towards the required products. Methanol is removed as the transesterification reaction of the dicarboxylic acid dimethyl ester progresses to shift the equilibrium towards the required products. In the esterification zone, monomer and oligomeric compounds (if any) are usually produced continuously in one or more reactors. Alternatively, the monomer and oligomeric compounds in the oligomeric mixture may be produced in one or more batch reactors. It is understood, however, that in the process of producing the PEN, the reaction mixture will contain the monomeric compound bis (2-hydroxyethyl) 2,6-naphthalene, and its corresponding oligomers. At this point, the It.V. typically not quantifiable or below 0.1 dL / g. The average degree of polymerization of the molten oligomeric mixture is usually below 15 and often below 7.0.

After the oligomeric mixture has been produced by achieving the required percentage of conversion of the acid and ester groups, it is usually transported by pipeline from the esterification zone or reactors to the polycondensation zone. The initiation of the polycondensation reaction is usually indicated by an actual operating temperature higher than the operating temperature in the esterification zone, or a significant drop in pressure (usually below atmospheric pressure) compared to the esterification zone, or both. Typical polycondensation reactions take place at temperatures ranging from about 260 ° C to 300 ° C and at subatmospheric pressures of about 350 mm Hg to 0.2 mm Hg. The residence time of the reactants in the reactor is typically from about 2 to about 6 hours. The polycondensation reaction produces a significant amount of glycol as a result of the condensation of oligomeric esters and the increase in molecular weight.

In some processes, polycondensation reactions are initiated and continued in a melt in a polycondensation zone with a pre-polymerization zone delineated and terminated in a melt in the end zone, whereupon the melt is solidified to form the melt polymerized polyester polymer, essentially in the form of chips, pellets or particles of any other shape. Each zone may include one or more separate reaction vessels operated under different conditions, or the zones may be combined in a single reaction vessel using one or more sub-stages operated under different conditions in a single reactor. That is, the prepolymerization step may involve the use of one or more continuously operated reactors, one or more batch reactors, and even one or more reaction steps or sub-steps performed in a single reactor vessel. The residence time of the alloy in the terminal zone relative to the residence time of the alloy in the prepolymerization zone is not limited. For example, in some reactor designs, the prepolymerization zone corresponds to the first half of polycondensation in terms of reaction time, and the end zone corresponds to the second half of the polycondensation. In other reactor designs, the residence time ratio in the end zone to the residence time in the prepolymerization zone can be adjusted to be about 1.5: 1 or greater. The prepolymerization and end zones often differ from one another in many designs in that the end zone typically has a higher operating temperature and / or lower operating pressure compared to the operating conditions of the prepolymerization zone. In general, each of the prepolymerization and end zones comprises one or more reaction vessels, and the prepolymerization and final reactors are arranged in series as part of a continuous polyester polymer production process.

Fig. 1 illustrates one embodiment of the present invention. The first alloy line consists of an esterification zone 101 and a polycondensation zone 102. There is no limit to a particular number of vessels or operating mode, and one of the many modes of operation has been described above. The product of the esterification zone 101 is preferably in fluid communication with the polycondensation zone 102 via a pipeline as shown, or by any other suitable method, for example via a central reservoir connecting the two zones.

The catalyst mixer 103 is the source of the first feed stream to the melt process. The first feed stream may be fed via pipeline 105 as the first feed stream to the melt line at any suitable point, or may be introduced into the melt line as a combo stream at any suitable point (discussed in more detail below). There is no limit to a specific addition point. As shown, the first feed stream can be introduced from the front end or at the start of the polycondensation zone, but it can also be introduced into the pipeline connecting the esterification zone to the polycondensation zone, or at the end of the esterification zone, or at any other desired point in the melt process.

The first feed stream is characterized by a constant (steady) molar ratio of the metal combination. At least two metals are used, and three, four or more metals may be used. For the sake of simplicity, reference is made to a mixture of metals A and B, but note that other metals can also be considered. Each metal is, alone or together with another metal in the first feed or second feed stream, a polycondensation catalyst or catalyst system (terms used interchangeably herein). Thus, taking metal A and metal B as an example, metal A is any metal that, together with metal B or alone, is a polycondensation catalyst, provided that metals A and B are not the same. Metals A and B may not be effective polycondensation catalysts when used alone, but together constitute an effective catalyst system, or only one of metals A and B may be effective as a polycondensation catalyst, but together they further increase the rate of polycondensation reaction. Alternatively, the catalytic activity of one of the metals may be too high such that, although the conversion is high and rapid, selectivity is low, resulting in many unfavorable by-products, and when combined with another metal, the catalytic system is moderated. Alternatively, one of the metals may not exhibit any catalytic activity. Any combination of metals combined for any reason is useful as long as the combination of metals as a system provides the catalytic activity of increasing the rate of the polycondensation reaction compared to the absence of all of these metals in the first feed stream and the second feed stream. While metals A and B are listed, the first feed stream may contain any number of additional metals.

The metals fed to the first feed stream may be added to the melt process as a solution, dispersion or slurry.

The source of the second feed stream is a metal reservoir 104. This reservoir contains metals whose number is less than all metals in the first feed stream, or a metal different from that in said first feed stream, or all metals that are the same as in said first feed stream. the first feed stream, but with a second molar ratio different from the said first molar ratio. Taking as an example only two metals A and B in the first feed stream, the metals tank 104 supplying the second feed stream contains only one of metals A or B, none of metals A and B, or both metals A and B in a second molar ratio different from of said first molar ratio. Each of these options is discussed in more detail.

The metal reservoir 104 is designed to be able to control the ratio of all catalytic metals (e.g. metals A and B) used in the production of the polyester polymer in the alloy line as required or required, increasing production flexibility to produce polymers with different properties, without having to wait for emptying of the inventory in the catalyst mixer 103 before making the change, to ensure on-going flexibility related to the regulation of catalyst ratios, when the produced polymer deviates from the specification, and to improve properties by adding portions of one or more metals at various points in the process. The process of the present invention also reduces the costs associated with maintaining two or even more catalyst mixers for polymer production using the required final molar ratio of the catalytic components.

Accordingly, a method of producing a polyester polymer in the melt line is presented which includes feeding a constant target amount of catalytic metals A and B from the catalyst mixer to the melt line and producing a polyester polymer with an amount of metal A exceeding the amount of metal A fed from the catalyst mixer to the melt process or the amount of metal B exceeding the amount of metal B fed from the catalyst mixer to the alloy process, or an amount of metals A and B greater than the amount of metals A and B fed from the catalyst mixer to the melt process, in each case without changing the target constant amount of metals A and B from the catalyst mixer to the melt line.

In the described further three embodiments, the first feed stream comprises metals A and B, for example, but it should be remembered that three or more metals may be present in the first feed stream.

In one embodiment, the catalyst mixer 103 contains metals A and B in a first ratio and the metal reservoir 104 contains only one of metals A or B, but not both. In this embodiment, other metals besides A and B may be included if desired. For example, the metals A and B in the catalyst mixer 103 may be Ti and Co, while the metal reservoir may contain Co or Ti or Co and Zn or Ti. and Zn, but not Co and Ti.

In a second embodiment, catalyst mixer 103 contains metals A and B in a first ratio, and the metal vessel 104 contains no metal A or B but contains metal C different from metals A and B. For example, metals A and B in catalyst mixer 103 may be Ti and Co, and the metal in the reservoir of metals may be Zn or Mg but not Ti or Co.

In the third embodiment, the catalyst mixer 103 contains metals A and B in a first ratio and the metal reservoir contains both metals A and B, but in a second molar ratio different from the first molar ratio. Thus, if the first molar ratio is 1: 1, the second molar ratio can be any but not 1: 1.

As mentioned above, three or more metals may be present in the first feed stream. Thus, in the first embodiment, the first feed stream may contain metals A, B, and C and the second feed stream may include metals A and B or A and C or B and C or only A, or only B, or only C. In a second embodiment using metals A, B, and C in the first feed stream, the second feed stream contains none of metals A, B, and C, but contains metal D, E, etc. In a third embodiment, the second feed stream comprises metals A, B and C, but in a different molar ratio than the first molar ratio.

The first stream is fed through pipeline 105 to the melt process line at any desired addition point in the melt line. Various directions for the introduction of the second feed stream into the stop line are possible. The second batch stream is fed:

(i) to one or more melt process lines before or after the point of addition of the first feed stream to the melt line; or (ii) to a first feed stream to one or more melt process lines, where said feed streams are combined. first and second, and then feeding the combined feed stream to one or more melt process lines. Option (i) is shown in Fig. 1, wherein the second feed stream on line 106 flows through line 107 and is added to the esterification zone 101 which is the addition point located upstream of the first feed stream addition point. Alternatively, the second feed stream on line 106 may flow through line 109 and be added to the polycondensation zone 102 at a point after the addition point of the first feed stream 105. If the second feed stream is fed at the point of addition after the first feed stream, it is preferably fed before the viscosity It.V. of the melt in the polycondensation zone will reach 0.3 dl / g or within about 20 minutes or about 10 minutes after the addition of the first feed stream, measured from time 0 when the polymer is combined with the first feed stream to the point where the flow occurs for a designated time or to the point in the reaction vessel where the polymer reacted for a designated time. Alternatively, the second feed stream in line 106 may flow through line 108 for addition to the conduit connecting the esterification zone 101 and polycondensation zone 102 at an addition point positioned as shown in the drawing upstream of the first feed stream addition point. If desired, the second batch stream can be introduced as little as 10 meters, or 5 meters, or 3 meters, or 1 meter from the point of addition of the first batch stream.

Option (ii) (not covered by the present invention) shown in Fig. 1 includes the flow of the second feed stream 106 through line 110 to connect to the first feed stream in line 105 at the junction point, before the first feed stream 105 is introduced into the melt line. The first feed stream and the second feed stream are combined at the joining point to form a combined feed stream, whereupon the combined feed stream is fed to any required addition point to the melt line.

The design of the second feed stream feed system may include one addition point to the stop line or multiple addition points to the stop line.

Fig. 2 shows another embodiment of the invention. In this embodiment, the catalyst mixer 203 supplies a plurality of melt lines, the first melt line comprises an esterification zone 201 and a polycondensation zone 202, and the second melt line comprises an esterification zone 201A and a polycondensation zone 202A. The first feed stream of catalytic metals is fed via lines 205 to the individual alloy lines. The metal reservoir 204 is the source of the second feed stream. The second feed stream is fed to one of the stop lines or a combination of more stop lines as required. For example, the second feed stream may only feed one but not both melt lines because the first melt line polymers are made using the first catalyst ratio and the second melt line polymers are made using the modified catalyst ratio and the modification is made by adding a second feed stream to the second stop line. Alternatively, if each line is producing different polymers, then the second feed stream may be fed to two or more melt lines.

As shown in Fig. 2, the second feed stream may be fed to one or both of the melt lines via line 206. As described above, the second feed stream may be added to the first melt line via any or more of lines 207, 208, or 209, it is also fed to the first feed stream to line 205 to obtain a combined stream fed to the first melt line. While the second feed stream is fed to the first stop line, the first feed stream is fed to both the first stop line and the second stop line. Optionally, the second feed stream may be metered or fed simultaneously to the second melt line at any point of addition 207, 208 and / or 209, or to the first feed line 205 to provide a combined feed to the second melt line.

This process is preferably carried out simultaneously. Preferably, the first and second alloy lines are operated in a continuous process. More preferably, the first feed stream and the second feed stream are fed continuously to at least the melt line, and if multiple melt lines are present, a single fixed first catalyst ratio catalyst reservoir supplies the first feed stream continuously to at least two melt lines, and the second feed stream is fed to one or at least two of said melt lines supplied by the first feed stream.

The molar ratio of metals in the first feed to the melt is preferably constant. The specific molar ratio is determined by the target molar ratio of the metals mixed in the catalyst mixer. The molar ratio of metals actually fed to the melt process in the first feed stream will be subject to slight fluctuations due to, inter alia, by variables such as potential precipitation or subsidence or replenishment of the catalyst mixer with fresh component catalysts while old stock remains in the mixer. However, the target metal molar ratio in the catalyst mixer is set each time the tank is refilled with component metals or, if the catalyst is continuously prepared in the mixer, the target molar ratio is kept constant for at least 5 days of production time.

In one embodiment, the catalytic metals in the catalyst mixer are at least aluminum and alkaline earth metal or an alkali metal such as sodium and / or lithium. The metal reservoir 106 or 206 contains one or more alkaline earth metals or alkali compounds, but no aluminum. Alkaline earth metals or alkali metals for the second feed stream, which can be added to the esterification zone before, during or after the esterification, or between the esterification zone and the polycondensation zone, or at the point where the polycondensation begins.

Catalytic metals A and / or B in the second feed stream according to the present invention may be added before 50% conversion of the reaction mixture to be esterified has taken place. In a further embodiment, the second feed stream is added to a paste making tank or to the paste feed of the esterification reactor or to the first esterification reactor.

The point of addition and / or the amount of the second feed stream can change the properties of the melt-produced polymer. For example, the addition of an alkaline earth metal or an alkali metal, in particular lithium, early in the process in the alloy, e.g. to the esterification zone, in particular to a paste preparation tank within the esterification zone, or at least before 50% conversion occurs, reduces the residual diethylene glycol (DEG) or DEG content of the melt-process polyester polymer. Reducing the DEG content is advantageous if the polymer is to be intended (suitable) for the production of heat stabilized blow molded bottles. Typical DEG content in a polyester polymer is about 2 mole percent for a continuous process. By adding lithium early in the melt process, for example, before 50% esterification (including transesterification) has taken place, the DEG content can be reduced compared to when lithium is not added to the esterification zone. The degree of reduction may be at least 10%, or at least 20%, or at least 30%.

The addition of metals A and / or B, such as alkaline earth metal or alkali metal, and in particular Li, to the melt process in the second feed stream increases the molar ratio of A: B, e.g. Li: Al, in the polyester polymer relative to the molar ratio A: B in the first batch stream.

Li: Al molar ratios in the polyester polymer of close to 1: 1 (e.g., from 0.5: 1 to 1.5: 1) are preferred because they enable the control of yellow inclusion formation in the polymer. Adding an amount of Li as the second feed stream which significantly increases the Li: Al molar ratio above 1: 1 in the polyester polymer, for example a 5: 1 ratio, will result in a significant yellow color of the polymer as determined by b * color measurements.

It may be advantageous to provide two melt lines, one of which produces a polyester polymer with a good b * color value of less than 5 or less than 4, or 3 or less, as determined by measurement with a preform made of this polymer. while the second melt line produces a polyester polymer with a low DEG content, e.g. less than 2 mole%. or 1.5 mole%. or less or 1 mole%. or less or 0.75 mole%. or less. In this embodiment, the catalyst mixer 203 supplies both lines with metals A and B, such as Li: Al, in a molar ratio of at least 0.5: 1, or at least 0.75: 1, or at least 0.8: 1. , or at least 0.9: 1 and up to 3: 1 or up to 2.5: 1, or up to 2: 1, or up to 1.7: 1, or up to 1.5: 1, or up to 1.3 : 1 or up to 1.2: 1 or up to 1.1: 1. In one embodiment, the Li: Al molar ratio ranges from 0.8: 1 to 1.5: 1, or from 0.9: 1 to 1.2: 1. The first alloy line is not supplied with a second feed stream, while the second is supplied with a second feed stream containing additional amounts of A or B metal, such as Li, sufficient to increase the molar ratio of A: B, such as Li: Al, by at least 25 %, or at least 35%, or at least 40%, or at least 50%, or at least 75%, or at least 90%, or at least 100%, or at least 150%, or by at least 200%, and up to about 2000%, or up to about 1000%, or up to about 500%.

In a further aspect, an amount of an alkaline earth metal or alkali metal, such as Na or Li, is added sufficient to increase the alkaline earth metal or alkali metal: Al ratio from 0.5: 1 to 2: 1 to the range from 3: 1 up to 10: 1 or 3: 1 to 7: 1 or 3: 1 to 5: 1.

Accordingly, a continuous process for the production of polyester polymers in at least two melt lines supplied by a common first batch of catalyst composition with a constant molar ratio has been presented, the polymers produced in at least one melt line having a catalyst ratio different from the ratio of catalysts in the first stream. batch. Thus, there is provided a method of producing polyester polymers involving the production of polyester polymer 1 in a melt 1 production line, said polyester polymer 1 containing metal A and metal B in a first A: B molar ratio, and polyester polymer 2 in a melt 2 production line, containing metal A and metal B in a second A: B molar ratio, metal A different from metal B, the molar ratios of polyester polymer 1 and 2 are different, and each of the production lines for alloy 1 and 2 is fed from a common catalyst mixer to feed metals A and B.

In one embodiment, the catalyst system comprises aluminum and at least one alkaline earth metal or alkali metal. The aluminum compound, and more broadly any of metals A or B, or both, are preferably added to the oligomer mixture, during or after esterification, or to the polyester melt no later than when the viscosity It.V. of the alloy reaches 0.3 dl / g, or no later than when the viscosity It.V. the melt reaches 0.2 dl / g, and more preferably to the oligomer mixture leaving the esterification zone or before the start of polycondensation.

The present invention enables the use of a first feed stream with an A: B molar ratio, e.g. alkaline earth metal or alkali metal: Al, in particular Li: Al, close to a molar ratio of 1: 1 (from 0.5: 1 to 1.5: 1 or from 0.75: 1 to 1.25: 1, or from 0.9: 1 to 1.1: 1), as a solution, suspension or dispersion system, to be added at any of the points mentioned, preferably after 90% conversion in the esterification process, followed by the addition of a second feed stream of metal A and / or B, e.g. containing an alkaline earth metal or an alkali metal such as Na or Li before or after the point of addition of the first feed stream, which will result in the final desired A: B molar ratio in the polyester polymer or the required alkaline earth metal or alkali metal: Al molar ratio . This method allows to obtain a catalyst activity very similar to that of a lithium-aluminum solution added at a standard addition point with the final required molar ratio. The present invention provides the flexibility to handle two alloy lines with two different catalyst molar ratios, having only one catalyst mix / feed system with a predetermined A: B metal ratio and supplying both lines with this catalyst mix / feed system.

Accordingly, the process of the present invention makes it possible to produce a polyester polymer in a melt line comprising feeding a fixed target amount of catalytic metals A and B from the catalyst mixer to the melt line and producing a polyester polymer with an amount of metal A exceeding the amount of metal A fed from the catalyst mixer to the process in the process. an alloy or amount of metal B exceeding the amount of metal B fed from the catalyst mixer to the alloy process, or an amount of metals A and B greater than the amount of metals A and B fed from the catalyst mixer to the melt process, in each case without changing the target constant amount of metals A and B from the catalyst mixer to the melt line. The melt line is preferably operated in a continuous process and has a throughput of at least 50 tons / day in a steady state operating mode.

Embodiments have been described where the catalyst system used as the first feed stream comprises Al and an alkaline earth metal or an alkali metal or one or more metals used in the second feed stream which are alkaline earth metals or alkali metals.

Aluminum may be added to the catalyst mixer as a compound (including salt or complex compound) or as an element, provided that it exhibits ultimate activity as a polycondensation catalyst, alone or in combination with an alkali metal or alkaline earth metal in the form of atoms or compounds .

In one aspect of the present invention, aluminum compounds with at least one or two or three organic substituents are used in preparing the composition. Exemplary aluminum compounds suitable for use as catalysts may have the following formula:

AI [OR]_and[OR ']_b[OR]_c[R ']_d where R, R, R are independently alkyl, aryl, acyl or hydrogen, R 'is an anionic, and a, b, c, d are independently 0 or positive integers, and a + b + c + d does not exceed 3, and is preferably 3.

Aluminum compounds exhibiting catalytic activity, as is the case with any metal compounds exhibiting catalytic activity during polycondensation reactions, include compounds capable of increasing the rate of polymerization reactions, particularly condensation reactions, such as those used to make polyester polymers (which can be measured as a reduction in processing time). to achieve the target It.V. viscosity or to increase the It.V. viscosity. over time, for example an increase of at least 0.1 dL / g per hour). The specific aluminum compounds selected are preferably compounds effective in increasing the It.V viscosity. the reactant alloy by at least 0.2 dl / g per hour.

It is also advantageous to use an aluminum compound with higher solubility in the solvent. Suitable examples of aluminum compounds include aluminum carboxylates such as aluminum acetate, aluminum benzoate, aluminum lactate, aluminum laurate, aluminum stearate, aluminum alkoxides such as aluminum ethoxide, aluminum isopropoxide, aluminum tri-n-butyrate, aluminum triisopropylate, tri-tert. - aluminum butyrate, mono-sec-butoxy aluminum diisopropylate and aluminum chelates in which the alkoxy group of the aluminum alkoxide is partially or fully substituted with chelating agents, such as alkyl acetoacetate or acetylacetate, e.g. aluminum ethylacetoacetate diisopropylate, aluminum tris (ethylacetate), aluminum alkylacetoacetate diisopropylate, aluminum monoacetoacetate bis (ethylacetoacetate), aluminum tris (acetoacetate), aluminum acetylacetonate.

Of the aluminum compounds, basic aluminum carboxylates and aluminum alkoxides are preferred. Basic aluminum carboxylates include monobasic and dibasic compounds. The basic aluminum acetate used may be a monohydric diacetate or dihydric monoacetate, or a mixture thereof. In one aspect, the aluminum compounds are aluminum acetate and aluminum triisopropylate. Aluminum triisopropylate is most preferred.

A certain number of aluminum atoms, in combination with a metal M (alkaline earth metal or alkali metal), are used to influence the polycondensation when added to the melt polymerization process. Suitable amounts of aluminum atoms present in the polymer generally range from at least 3ppm, or at least 5ppm, or at least 10ppm, or at least 15ppm, or at least 20ppm, or at least 30ppm, to about 150ppm or up to about 100 ppm, or up to about 75 ppm, or up to about 60 ppm aluminum atoms, based on the weight of the polymer.

The preferred range of the amount of aluminum in the polyester polymer as well as the amount of aluminum atoms present in the composition fed to the melt polymerization reactor suitable for inclusion in the polymer is from 5 ppm to 60 ppm, and the most preferred amount calculated is from 10 to 20 ppm Al based on the weight of the polymer. . Of course, the composition of the first feed stream can, and usually does, contains a much higher concentration of metals than that found in the polyester polymer. This composition is fed or metered into the melt at a rate corresponding to the required amount of metal present in the polyester polymer. The composition may contain from 1000 ppm, or at least 2000 ppm, or greater than 3000 ppm, or at least 3500 ppm, or at least 4000 ppm, or at least 5000 ppm, or at least 1 wt.%. The maximum amount of aluminum used corresponds to the limit of its solubility in a given mixture of solvents under ambient conditions. High concentrations of aluminum are preferred so that the amount of solvent fed to the melt process is reduced and / or larger amounts of aluminum can be fed to the melt for the production of the polyester polymer at a specific flow rate to increase the rate of polycondensation reaction and therefore including shortening the polymerization time and increasing the yield.

In one embodiment, a catalyst solution is provided containing at least 3,000 ppm aluminum, or at least 3,500 ppm aluminum, or at least 4,000 ppm aluminum, or at least 10,000 ppm, which may contain up to 10 wt. or up to 5 wt.%. or up to 3 wt.%. or up to 2 wt.%. aluminum. Solution means a composition capable of remaining in a dissolved state for a period of at least (1) weeks without formation of visible precipitate when standing under ambient conditions (temperature ranging from 25 ° C to 40 ° C).

An alkali metal can be added as a metal compound or an organometallic compound. The alkali metals and alkaline earth metals include metals from group IA and group IIA of the periodic table, including Li, Na, K, Rb, Cs, Mg, Ca, Sr and preferably Li, Na or K. When high speed is essential, Li or Na is generally preferred. If color is the primary concern, Na is most preferred. The metals can be added to the alloy in the form of metal compounds (including complexes or salts) containing counter ions, of which hydroxides, carbonates, and carboxylic acids are preferred. The amount of alkaline earth metal or alkali metal, when combined with Al, effectively increases the molecular weight of the polymer alloy. The amount by weight varies significantly with the molecular weight of the metal. The amount of alkaline earth metal or alkali metal in the composition may be from at least 250 ppm, or at least 500 ppm, or at least 700 ppm, or at least 780 ppm, or at least 1000 ppm, or at least 2000 ppm, or at least 2460 ppm. ppm, or at least 3000 ppm, or at least

5000 ppm, or at least 1 wt.%, or at least 2 wt.%, up to about 30 wt.%. or up to about 20 wt.%, or up to about 15 wt.%, or up to 10 wt.%, or up to 5 wt.%, or up to 2 wt.%, or up to 1 wt.%, or up to 5000 ppm, based on mass of the solution. The amount of alkaline earth metal or alkali metal fed to the melt polymerization process enables the efficient production of a polyester polymer composition comprising, wherein the polyester polymer composition comprises, from at least 1 ppm, or at least 2 ppm, or at least 3 ppm, or at least 4 ppm , or at least 5 ppm, up to about 60 ppm, or up to about 50 ppm, or up to about 30 ppm, or up to about 20 ppm, or up to about 15 ppm, of an alkaline earth metal or an alkali metal, the amount of which was calculated based on the weight of the polyester polymer composition. The specific amount of the alkaline earth or alkali metal in the polyester polymer varies with the molecular weight of the metal.

A solution, dispersion or suspension is prepared by combining metal compounds, e.g. alkaline earth metal or alkali salts with aluminum compounds, preferably with a trivalent aluminum compound, and with a suitable solvent such as ethylene glycol, DEG, polyhydric alcohol ethers or monohydric alcohol ethers, or a combination thereof, or any other suitable solvent, and stirring the mixture at a temperature ranging from 20 ° C to 150 ° C or from 80 ° C to 140 ° C.

In the vessel, the alkaline earth metal or the alkali metal may be dissolved in water or any other suitable solvent.

While a catalyst mixer 103 and a metal reservoir 104 are described, the method of the present invention may include any other device upstream or downstream of these tanks, for example, upstream batch vessel, metering devices, valves, and pumps.

Preferably, a phosphorus compound is also added to the melt polymerization process, the catalyst stabilizer being added to the polyester melt late in the polycondensation process, prior to solidification. The deactivator is added to the polyester melt at a late stage in the course of the polycondensation reaction when at least one of the following conditions is met, or after polycondensation, and before solidifying the polyester melt: a) the polyester melt reaches its It.V. viscosity. of at least 0.50 dL / g or

(b) there is at least a partial release of the negative pressure applied to the polyester alloy, if applicable, or

(c) if the polyester melt is present in a melt polymerization process, the addition of a phosphorus compound within the post-reactor for making the polyester polymer near its discharge point or between the post-reactor and the polyester melt cutter; or

(d) if the polyester melt is present in a melt polymerization process, at least 85% of the time required for the polycondensation of the polyester melt, or

e) It.V. viscosity of the polyester alloy is +/- 0.15 dl / g of It.V. viscosity. obtained after solidification or

f) at a point within 30 minutes or less, or 20 minutes or less, after the polyester alloy has solidified.

In one embodiment, the deactivator is added to the polyester melt after the polyester melt has an It.V. viscosity. of at least 0.50 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 0.76 dL / g, or at least 0.78 dL / g, with most preferably, regardless of when the deactivator is added, the resulting polymer after melt production has a viscosity It.V. of at least 0.68 dL / g, or at least 0.72 dL / g, or at least 0.76 dL / g.

In a further embodiment, the deactivator is added to the polyester melt during or after the depressurization of the polyester melt to be subjected to the polycondensation reactions or after pressurization of the polycondensation zone or reactor from a lower level of at most 10 mm Hg or less, or preferably from a lower level of at most 3 mm Hg or less to a level of 300 mm Hg or more, or 450 mm Hg or more, or 600 mm Hg or more, or to or above atmospheric pressure, preferably before solidification of the polyester melt occurs.

In a further embodiment, the deactivator is added at or near the end of the post reactor or between the post reactor and the cutter. For example, the deactivator is added at least to the polycondensation reactor proximal to the outlet of the last polycondensation reactor or to the pipeline connecting directly or indirectly the last polycondensation reactor and the gear pump or extruder providing the driving force for pushing the melt through the die plate, said pipeline pointing backwards. or proximal to the outlet or bottom of the last polycondensation reactor, or to the inlet of the pipeline to the last polycondensation reactor located proximally to its outlet. The location proximal to the outlet of the last polycondensation reactor means that the addition site is within a maximum of the last 25% of said reactor or a maximum of the last 15% of said reactor, or preferably within a maximum of the last 10% of said reactor. The percentage may refer to the length, height or volume of the polycondensation reactor. Preferably the percentage relates to length or height.

The latter, expressed as a percentage of length, height or volume, are measured starting from the outlet of the last polycondensation reactor.

In yet another embodiment, the deactivator is added to the polyester melt after at least 85%, or at least 90%, or at least 95%, or at least 98%, or about 100% of the average polycondensation time. The average polycondensation time is a measure of the average time that elapses from the moment a certain portion of the alloy enters the polycondensation zone to the moment that that particular portion of the alloy reaches the outlet of the polyester alloy from the last polycondensation reactor. The mean polycondensation time or the mean residence time in the polycondensation zone can be measured by index tests or modeling. In another embodiment, the deactivator is added to the polyester melt when the It.V. The polyester alloy is in the range of 0.15 dL / g, or in the range of 0.10 dL / g, or in the range of 0.05 dL / g, or in the range of 0.030 dL / g, or in the range of 0.02 lt.V viscosity . obtained after solidification.

For example, the polyester alloy may have an It.V. viscosity. 0.10 dL / g below the It.V. viscosity obtained after solidification, or it may have an It.V. 0.10 dL / g above It.V. obtained after solidification.

In yet another embodiment, the deactivator is added to the polyester melt at a point within 30 minutes or sooner, within 20 minutes or earlier, or within 10 minutes or earlier, or 5 minutes or earlier, or 3 minutes or earlier, of solidification of the polyester melt. . Solidification of the polyester melt typically occurs when the melt is forced through a waterbath die plate and cut into pellets or, in the case of a melt-to-mold process, when the alloy is injection molded into the final product. In the broadest sense, solidification occurs when the temperature of the polymer melt is reduced below the melting point of the polymer crystals.

In an even more preferred embodiment, each of the embodiments defined herein are separately or in combination in a continuous production process wherein the melt yield is at least 1 metric ton / day, or at least 50 metric tons / day, or at least 100 metric tons / day. metric tons / day or at least 200 metric tons / day or at least 300 metric tons / day or at least 400 metric tons / day or at least 500 metric tons / day of polyester polymer in a steady state mode of operation.

Melt reaction time from viscosity It.V. of 0.40 dL / g to an It.V. in the range of at least 0.68 dL / g to 0.94 dL / g is preferably 240 minutes or less, 210 minutes or less, 180 minutes or less, 150 minutes or less, or 120 minutes or less, or 90 minutes or less , or 50 minutes or less. At the given time, a negative pressure of preferably from 0.5 to 1.0 mm Hg is applied, and the temperature is preferably from 275 ° C to 285 ° C. Target Viscosity It.V. it is preferably from 0.82 to 0.92 dl / g before deactivation / stabilization.

It should be noted that the melt process conditions and reactor configurations described above are intended to illustrate the melt process and that the present invention is not limited to this illustrative process. For example, although reference is made to different operating conditions with specific distinct It.V. values, other process conditions may be used within the given It.V. or otherwise, or the specified operating conditions can be applied under points It.V. alloy other than specified. In addition, you can adjust the process conditions based on reaction time instead of measuring or predicting It.V. alloy. The process is also not limited to the use of in-line or parallel reactors or the use of different vessels in different zones. Nor is it necessary to separate the polycondensation reaction into a prepolymerization zone and an end zone, since the polycondensation reaction can take place in a single polycondensation reactor using different operating conditions over time or in multiple reactors arranged in series, operating batchwise, semi-batch or in a continuous process.

After obtaining the required It.V. The molten polyester polymer in the melt reactors is evacuated as a melt product, then cut and solidified. The polyester polymer product in the melt is melt processed into the required form such as amorphous particles; however, crystallized granules are preferred. There is no restriction on the shape of the polyester polymer particles, they can be discrete particles of regular or irregular shape, without being limited in size, such as stars, spheres, spheroids, globoids, cylindrical-shaped granules, conventional granules, pellets, or particles of any other shape. the particles being distinct from sheet, foil, preforms, strands or fibers.

There are no particular restrictions on the number-average weight (not to be confused with the number-average molecular weight) of the particles. Preferably, the particles have a number average weight of at least 0.10 g per 100 particles, preferably greater than 1.0 g per 100 particles, and up to about 100 g per 100 particles.

There is no restriction on how the polyester polymer is solidified from the melt process. For example, the melt polyester polymer from the melt process can be guided through the die or can only be cut, or the molten polymer can be guided through the die and then cut. A gear pump may be used to provide the driving force for the molten polyester polymer through the die.

Instead of using a gear pump, the molten polyester polymer may be fed to a single screw or twin screw extruder and extruded through the die, optionally at a temperature of 190 ° C or higher within the extruder die. After passing through the die, the polyester polymer can be formed into strands by drawing, brought into contact with a cool fluid and cut into granules, or the polymer can be pelleted within the die head, optionally under water. The polyester polymer melt is optionally filtered prior to cutting to remove particulates exceeding a designated size. Any conventional hot pelletizing or dicing method and equipment may be used, including but not limited to dicing, pelletization of strands and pelletization of strands with forced flow, tablet presses, water ring pelletizers, pelletizers with heated face surfaces, underwater pelletizers and pelletizers with centrifugation function.

The polyester polymer has the ability to crystallize. There are no restrictions on the method and apparatus for the crystallization of the polyester polymer. thermal crystallization in gas or liquid. Crystallization can take place in a mechanically agitated vessel; in a fluidized bed; in a bed mixed by fluid movement; in a tank without agitation or pipeline; in a liquid medium at a temperature above the Tg of the polyester polymer, preferably at a temperature of 140 ° C to 190 ° C, or by any other method known in the art. The polymer can also crystallize under stress. Alternatively, the polymer may be fed to the crystallizer where the polymer temperature is below its Tg temperature (glass transition temperature), or it may be fed to the crystallizer where the polymer temperature is above its Tg temperature. For example, the polymer melt from the melt polymerization reactor may be passed through a die plate and cut under water, followed immediately by an underwater thermal crystallization reactor in which the polymer is subjected to underwater crystallization. Alternatively, the polymer melt may be cut, allowed to cool below the Tg temperature, and then fed to an underwater thermal crystallization device or any other suitable crystallization device. Alternatively, the polymer melt may be cut in any conventional manner, allowed to cool below the Tg temperature, optionally stored, and then crystallized.

The degree of crystallinity is optionally at least 30%, or at least 35%, or at least 40%.

Suitable polyesters include polyesters containing arylated alkylene repeats such as polyalkylene terephthalate or naphthalene. In one embodiment, the polyester polymer comprises:

(a) a carboxylic acid component containing at least 90 mole%. or at least 92%, or at least 96 mole%. terephthalic acid residues, terephthalic acid derivatives, naphthalene-2,6-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid derivatives or mixtures thereof, more preferably terephthalic acid or terephthalic acid derivatives, and (b) a hydroxyl component containing at least 90 mole%. or at least 92 mole%, or at least 96 mole%. ethylene glycol or propanediol residues, more preferably ethylene glycol, based on 100 mole percent of carboxylic acid component residues and 100 mole percent of hydroxyl component residues of the polyester polymer. The reaction of the carboxylic acid component with the hydroxyl component in the preparation of the polyester polymer is not limited to the stated mole percentages, since a large excess of the hydroxyl component, e.g. on the order of up to 200 mole%. relative to 100 mol%. the carboxylic acid component used. The polyester polymer resulting from this reaction, however, will contain the stated amounts of aromatic dicarboxylic acid residues and ethylene glycol residues.

Derivatives of terephthalic acid and naphthalenedicarboxylic acid include C1-C4 dialkyl terephthalates and C1-C4 dialkyl naphthalates such as dimethyl terephthalate and dimethyl naphthalate.

Modifiers may be present up to 40 mole%. or up to 20 mole%, or up to 10 mole%, or up to 8 mole%, or up to 4 mole%. based on all moles of the corresponding polymer component. One, three, and more functional modifiers are preferably present in amounts of only up to about 8 mol%. or up to about 4 mole%.

In addition to the diacid terephthalic acid component, terephthalic acid derivatives, naphthalene-2,6-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid derivatives or mixtures thereof, the carboxylic acid components of the present polyester may include at least one additional carboxylic acid modifier compound . Such additional carboxylic acid modifier compounds include monocarboxylic acid compounds, dicarboxylic acid compounds, and compounds with more carboxylic acid groups. Examples include aromatic dicarboxylic acids preferably containing from 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably containing from 4 to 12 carbon atoms or cycloaliphatic dicarboxylic acids preferably containing from 8 to 12 carbon atoms. More specific examples of modifier dicarboxylic acids suitable for use as acid components include: phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid , succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like, the most preferred being: isophthalic acid, naphthalene-2,6-dicarboxylic acid, and cyclohexane-1,4-dicarboxylic acid. It should be understood that the use of the corresponding acid anhydrides, esters and acid chlorides of these acids is included in the term "carboxylic acid". The polyester can also be modified by tricarboxylic branching agents and compounds with more carboxylic acid groups as well as monocarboxylic chain end groups.

In addition to the hydroxyl component of ethylene glycol, the hydroxyl component of the present polyester can include additional modifiers, polyhydric alcohols, diols, or compounds with more than one hydroxyl group. Examples of hydroxyl modifier compounds include cycloaliphatic diols preferably containing from 6 to 20 carbon atoms and / or aliphatic diols preferably containing from 3 to 20 carbon atoms. More specific examples of such diols include: diethylene glycol; triethylene glycol; 1,4 cyclohexanedimethanol; propane-1,3-diol; butane-1,4-diol; pentane-1,5-diol; hexane-1,6-diol; 3-methylpentanediol- (2,4); 2-methylpentanediol- (1,4); 2,2,4-trimethylpentane diol (1,3); 2,5-ethylhexanediol- (1,3); 2,2-diethylpropane-diol- (1,3); hexanediol- (1,3); 1,4-di (hydroxyethoxy) benzene; 2,2-bis- (4-hydroxycyclohexyl) propane; 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane; 2,2-bis- (3-hydroxyethoxyphenyl) propane and 2,2-bis- (4-hydroxypropoxyphenyl) propane.

As modifiers, the polyester polymer may advantageously contain comonomers such as isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedimethanol, and diethylene glycol.

The polyester composition may contain mixtures of polyalkylene terephthalates and / or polyalkylene naphthalates along with other thermoplastic polymers such as polycarbonate (PC) and polyamides. Preferably, the polymer composition should contain the majority of the polyester polymers, more preferably in an amount of at least 80 wt.%. or at least 95 wt.%, most preferably 100 wt.%, based on the weight of all thermoplastic polymers (excluding fillers, inorganic compounds or particles, fibers, impact modifiers, or other polymers that may form a discontinuous phase). It is also preferred that the polyester polymers do not contain any fillers, fibers, impact modifiers, or other polymers that make up the discontinuous phase.

In one embodiment, the composition comprises less than 60 wt. or less than 40 wt.%, or less than 20 wt.%, or less than 10 wt.%, or less than 5 wt.%, or no post-recycled polyester polymer ("PCR").

In another embodiment, the composition comprises a PCR polymer in an amount greater than zero to 60 wt%. or up to 40 wt.%, or up to 20 wt.%, or up to 10 wt.%.

The particles of the present invention are directly or indirectly packed as loads in shipping containers which are then shipped to customers or distributors. It is preferable to subject the crystallized particles to any process according to the embodiment described herein without the solid state polymerization of the particles at any time prior to packaging the particles in shipping containers. Except for solid state polymerization, the particles may undergo a number of additional processing steps between any of the steps mentioned.

Shipping containers can be containers for land, sea or air transportation. Examples include wagons, trailer containers, cardboard containers, ship hulls, or any other container used to transport the final polyester particles to the customer. Customers are typically those processing these particles into preforms or other formed articles.

Shipping containers contain a load of polyester polymer particles. Such a load takes a volume of at least 3 cubic meters. In preferred embodiments, the cargo in the shipping container occupies a volume of at least 5 cubic meters, or at least 10 cubic meters.

In one embodiment, the final particles of a polyester polymer of medium viscosity, It.V. are provided. of at least 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 is obtained by melt polymerization having a residual acetaldehyde level of 10 ppm or less, or 5 ppm or less; wherein said particles contain aluminum at a level of at least 3 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15 ppm, or at least 20 ppm, based on the weight of the polymers. Preferably, the polyester particles in the shipping container also have a degree of crystallinity of at least 20%, preferably of at least 30%; in addition, the particles also contain greater than zero levels of alkaline earth metal or alkali metal, along with greater than zero levels of phosphorus. More preferably, the AA (acetaldehyde) production index 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 in addition a brightness value The L * of the particles is at least 55, or at least 60, or at least 65, or at least 70, or at least 73, or at least 76, and the particles do not contain AA absorbers. The particles are preferably in a shipping container. Most preferably, the particles have not been solid state polymerized. The term "final" particles means that the particles have been subjected by the particle manufacturer to all processing conditions needed to produce a particle ready for inclusion into the chute of a dryer attached to the molding machine or directly into the molding machine used to convert the particles into articles, without further processing steps by the particle manufacturer.

Articles may be formed from alloyed products by any conventional techniques known to those skilled in the art. For example, melt-derived products, optionally solid-state polymerized, crystallized to a degree of crystallinity of at least 20%, are introduced into equipment for extruding the melt and injection molding it into shapes such as preforms suitable for stretch blow molding into containers for beverages and food, or for injection molding equipment, or for equipment used solely for extrusion into other forms, such as a sheet. Suitable known product forming processes include extrusion, extrusion blow molding, melt casting, injection molding, melt-to-mold, stretch blow molding (SBM), thermoforming, etc.

Examples of shaped articles that can be formed from the melt-obtained products and the polyester polymer composition of the present invention include: sheet; foil; packaging and containers such as preforms, bottles, jars and trays; rods; tubes; lids and stamens and fibers. Beverage bottles made of polyethylene terephthalate suitable for containing water and carbonated beverages, and heat stabilized beverage bottles suitable for containing beverages when hot introduced into these bottles are examples of bottles made of crystallized granules in accordance with the present invention. Examples of trays include microwave suitable dual trays and other CPET trays. Each of the embodiments defined herein may, if desired, be present in a continuous production process where the melt throughput is at least 1 ton / day, or at least 50 tons / day, or at least 100 tons / day, or at least 200 tons / day, or at least 300 tons / day, or at least 400 tons / day, or at least 500 tons / day, of the polyester polymer in a steady state mode of operation.

Melt reaction time from viscosity It.V. of 0.40 dL / g to an It.V. in the range of at least 0.68 dL / g to 0.94 dL / g is 150 minutes or less, or 120 minutes or less, or 90 minutes or less, or 50 minutes or less. Target Viscosity It.V. is preferably 0.84 to 0.94 dl / g before deactivation / stabilization, the applied vacuum is preferably 0.5 to 1.0 Tr, and the temperature is preferably 275 to 285 ° C. The present invention may also be illustrated by means of additional embodiments thereof, however, it should be noted that the accompanying examples are for illustrative purposes only and do not limit the scope of the present invention.

Examples

Source of oligomers: Oligomers obtained using a Parr reactor. Some of them contained LiOH * H2O or Al (O'Pr) 3 (see Table 1 below).

Preparation of the lithium-aluminum solution: The compounds LiOH * H2O and Al (O'Pr) 3 were used as the sources of catalytic metals. The solutions were prepared by combining the appropriate amount of the individual catalytic compounds in ethylene glycol to achieve the required Li: Al molar ratio and a total aluminum concentration of 3000 ppm by weight. The solutions were heated to 125 ° C and purged with nitrogen to remove any low boiling volatiles. The 1: 1 Li: Al solution was set aside to precipitation and added to the polymerization process as a slurry.

Polymerization Procedure: Standard 1/2 molar equipment configuration was used for each polymerization. 113 grams of oligomer was added to each 500 mL round bottom flask and the Camile sequence shown below was started. Catalyst solution was added in step 3 and excess LiOH * H 2 O in EG (as reported) was added 10 or 20 minutes after the first catalyst addition. The target Al load was 15 ppm in all cases. In cases where no additional lithium was added, ethylene glycol was added 20 minutes after the catalyst solution to keep the total EG charge in the system consistent. All series ended with torque with an actual torque value of 6.0. The time in the post reactor is given as the initial indication of catalyst activity.

Charges and sequence in the Parr reactor: TPA: 1628 g

IPA: 33 g

EG: 869 g

LiOH * H2O: 0.2 g (19 ppm) when necessary

Al (O'Pr) s: 0.2 g (15 ppm), when necessary

<td>Stage</td><td>time (min)</td><td>RPM</td><td>psig ^(Tr)</td><td>Temp. - tank (° C)</td><td>Temp. - column (° C)</td>

<td> 1</td><td> 0,1</td><td> 0</td><td> 0</td><td> 25</td><td> 25</td>

<td> 2</td><td> 5</td><td> 180</td><td> 40</td><td> 25</td><td> 25</td>

<td> 3</td><td> 0,1</td><td> 180</td><td> 40</td><td> 240</td><td> 25</td>

<td> 4</td><td> 45</td><td> 180</td><td> 40</td><td> 240</td><td> 25</td>

<td> 5</td><td> 0,1</td><td> 180</td><td> 40</td><td> 240</td><td> 150</td>

<td> 6</td><td> 15</td><td> 180</td><td> 40</td><td> 240</td><td> 150</td>

<td> 7</td><td> 180</td><td> 180</td><td> 40</td><td> 240</td><td> 150</td>

<td> 8</td><td> 30</td><td> 180</td><td> 0</td><td> 240</td><td> 150</td>

Camile Sequence:

<td>Stage</td><td>Time (min)</td><td>Temp. (° C)</td><td>Vacuum (Tr)</td><td>Agitation (rpm)</td><td>Comments</td>

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

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

<td> 3</td><td> 1</td><td> 265</td><td> 730</td><td> 150</td><td>Addition of Li / Al solution</td>

<td> 4</td><td> 2</td><td> 265</td><td> 330</td><td> 300</td><td></td>

<td> 5</td><td> 2</td><td> 265</td><td> 330</td><td> 300</td><td>Calibrating the agitator</td>

<td> 6</td><td> 6</td><td> 278</td><td> 30</td><td> 300</td><td></td>

<td> 7</td><td> 44</td><td> 278</td><td> 30</td><td> 300</td><td></td>

<td> 8</td><td> 2</td><td> 278</td><td> 30</td><td> 300</td><td></td>

<td> 9</td><td> 1</td><td> 278</td><td> 30</td><td> 200</td><td></td>

<td> 10</td><td> 20</td><td> 278</td><td> 30</td><td> 200</td><td></td>

<td> 11</td><td> 2</td><td> 278</td><td> . 4</td><td> 200</td><td></td>

<td> 12</td><td> 60</td><td> 278</td><td> 4</td><td> 200</td><td></td>

<td> 13</td><td> 2</td><td> 278</td><td> 0,8</td><td> 30</td><td></td>

<td> 14</td><td> 500</td><td> 278</td><td> 0,8</td><td> 30</td><td>Termination by torque</td>

The results are shown in Table 1.

Table 1

<td>A sample</td><td>The molar ratio of the solution Li / Al</td><td>Li equivalents added separately</td><td>Li addition point</td><td>Ultimately target Li / Al molar ratio</td><td>Final reactor time m (min)</td><td>IhV</td><td>DEG (wt%)</td><td>Li (ppm)</td><td>Al (ppm)</td>

<td> 1</td><td> 1:1</td><td> 4</td><td>Po Li / Al</td><td> 5:1</td><td> 142,6</td><td> 0,888</td><td> 4,24</td><td> 23</td><td> 18</td>

<td> 2</td><td> 1:1</td><td> 4</td><td>Po Li / Al</td><td> 5:1</td><td> 87,5</td><td> 0,832</td><td> 4,36</td><td> 19</td><td> 25</td>

<td> 3</td><td> 1:1</td><td> 4</td><td>Po Li / Al</td><td> 5:1</td><td> 99,3</td><td> 0,853</td><td> 4,37</td><td> 30</td><td> 15</td>

<td> 4</td><td> 1:1</td><td> 4</td><td>Po Li / Al</td><td> 5:1</td><td> 124,4</td><td> 0,834</td><td> 4,19</td><td> 25</td><td> 13</td>

<td> 5</td><td> 1:1</td><td> 4</td><td>Po Li / Al</td><td> 5:1</td><td> 84,4</td><td> 0,885</td><td> 4,42*</td><td> 24</td><td> 18</td>

<td> 6</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 80,7</td><td> 0,871</td><td> 4,34</td><td> 18</td><td> 16</td>

<td> 7</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 124,3</td><td> 0,862</td><td> 4,77</td><td> 20</td><td> 17</td>

<td> 8</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 105,1</td><td> 0,861</td><td> 4,42</td><td> 12</td><td> 15</td>

<td> 9</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 128,8</td><td> 0,876</td><td> 4,35</td><td> 19</td><td> 16</td>

<td> 10</td><td> 1:1</td><td> 4</td><td>Esterification</td><td> 5:1</td><td> 129,8</td><td> 0,906</td><td> 1,64</td><td> 18</td><td> 16</td>

<td> 11</td><td> 1:1</td><td> 4</td><td>Esterification</td><td> 5:1</td><td> 107,3</td><td> 0,876</td><td> 1,65</td><td> 18</td><td> 19</td>

<td> 12</td><td> 1:1</td><td> 4</td><td>Esterification</td><td> 5:1</td><td> 66,0</td><td> 0,804</td><td> 1,76</td><td> 17</td><td> 15</td>

<td> 13</td><td> 1:1</td><td> 4</td><td>Esterification</td><td> 5:1</td><td> 73,3</td><td> 0,814</td><td> 1,80</td><td> 14</td><td> 16</td>

<td> 14^and</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 333,4</td><td> 0,767</td><td> 1,06</td><td> 40</td><td> 10</td>

<td> 15^and</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 249,2</td><td> 0,793</td><td> 1,45</td><td> 19</td><td> 13</td>

<td> 16^and</td><td> 5:1</td><td> 0</td><td>Not applicable</td><td> 5:1</td><td> 241,0</td><td> 0,728</td><td> 1,49</td><td> 18</td><td> 13</td>

<td> 17</td><td>Only Al</td><td> 4</td><td>Esterification</td><td> 4:1</td><td> 237,4</td><td> 0,858</td><td> 1,60</td><td> 14</td><td> 13*</td>

<td> 18</td><td> 1:1</td><td> 0</td><td>Not applicable</td><td> 1:1</td><td> 126,3</td><td> 0,854</td><td> 4,61</td><td> 4</td><td> 18*</td>

<td> 19</td><td> 1:1</td><td> 0</td><td>Not applicable</td><td> 1:1</td><td> 154,2</td><td> 0,903</td><td> 4,13</td><td> 4</td><td> 16</td>

<td> 20</td><td> 1:1</td><td> 0</td><td>Not applicable</td><td> 1:1</td><td> 149,4</td><td> 0,889</td><td> 4,25</td><td> 4</td><td> 17</td>

^andFor the 14-16 batch, Li and Al were added to the Parr reactor during the esterification process. The series were manually terminated before reaching the target torque. Li addition point definitions:

"Po Li / Al": The Li solution was added 10-20 minutes after the addition of the Li / Al catalyst solution. "Esterification": Li was added during the esterification process in the Parr reactor.

Li equivalents were determined against the amount of Al added expressed in moles *, returned for analysis and corrected

Table 2 shows the mean values ​​for the above series.

Table 2

<td>Description</td><td>Number of series</td><td>Time in post reactor (min)</td><td>IhV</td><td>DEG (wt%)</td><td>Li (ppm)</td><td>^Al (ppm)</td>

<td>1: 1 Li / Al + 4 Li later</td><td> 5</td><td> 107,6</td><td> 0,854</td><td> 4,32*</td><td> 24,2</td><td> 19,8</td>

<td>5: 1 Li / Al</td><td> 4</td><td> 109,7</td><td> 0,868</td><td> 4,47</td><td> 17,3</td><td> 16,0</td>

<td>1: 1 Li / Al + 4 Li during esterification</td><td> 4</td><td> 94,1</td><td> 0,850</td><td> 1,71</td><td> 16,8</td><td> 16,5</td>

<td>5: 1 Li / Al was added during esterification</td><td> 3</td><td> 274,5</td><td> 0,763</td><td> 1,33</td><td> 25,7</td><td> 12,0</td>

<td>4 Li during esterification, only Al at the usual time</td><td> 1</td><td> 237,4</td><td> 0,858</td><td> 1,60</td><td> 14,0</td><td> 55,0</td>

<td>1: 1 Li / Al</td><td> 3</td><td> 143,3</td><td> 0,882</td><td> 4,33</td><td> 4,0</td><td> 19,3</td>

<td colspan="2">* submitted again for analysis and is</td><td colspan="5">original</td>

The results from these data indicate that the first three systems are similar in activity. A Li: Al ratio of 5: 1 can be obtained in many ways, and the performance of such solutions is similar. As mentioned above in one embodiment, it is possible to lower the DEG content using the method of the present invention. As stated above, the DEG content is significantly lower when the 4 Li solution is added during the esterification. In a batch process, the initial content of DEG is high, therefore the effect of reducing the amount of DEG is high. For continuous production lines, a reduction in the DEG content is also expected, but the impact will then not be as significant as the controlled DEG content is typically in the range of 2-3 mole percent.

The control for the 1: 1 ratio Li / Al solution is clearly slower than for any of the series with the 5: 1 ratio Li / Al solution. Complete separation of Li and Al (5th position in this table, 17th position above) leads to very poor catalytic activity. The addition of a 5: 1 Li / Al solution in the esterification step is not effective.

796 741.2 September 2016

r.

GRUPO PETROTEMEX, SA de CV 106073P511PCEP

MR / ABB