Broad mwd, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom
Abstract
The present invention deals with a continuous process and polymerization system characterized by a separate incorporation of catalyst and a surplus of water, an ethylene interpolymer composition characterized in that it has a wide molecular weight distribution (MWD) and the optimization of the homogeneity of its structure, a process for the manufacture of such a composition and an article manufactured thanks to that composition. The new composition is characterized in that it has a melting point ratio 10 2, from 8 to 10.4, an Mw / Mn ratio greater than 4 as determined by gel chromatography, a melting index I2 of 0.1 to 10 grams / 10 minutes, a density less than 0.945 grams / cubic centimeter, and based on the total weight of the crystallizable polymer parts, a weight percentage of the dominant peak temperature greater than 75 0 C, as determined by fractionation of crystallographic analysis in the range of 20 to 100 0 C, equal to or greater than the mathematical product of 1.7946x10 -28 x 10 31.839 x density of the composition, a density of the composition in grams / cubic centimeters The new composition shows good processability and improved toughness properties, especially excellent resistance of the film to breakage and impacts, and is particularly applied for use in applications such as the long-lasting coating of the interior of garbage containers and the making of very resistant bags.

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19 claims: 3 independent, 16 dependent
- 1ES 2 178 232 T5 REIVINDICACIONES 1. Un procedimiento que se lleva a cabo en un sistema de polimerización de etileno para preparar una composición de polímero de etileno, comprendiendo el sistema al menos dos puntos de inyección y al menos dos reactores de polimerización, teniendo cada reactor una corriente o zona de reacción en la que se inyecta al menos un sistema catalítico y alimentación de nuevo aporte, en la que la alimentación de nuevo aporte comprende etileno y opcionalmente al menos un comonómero insaturado, comprendiendo el procedimiento operar en continuo los al menos dos reactores de polimerización e inyectar separadamente el sistema catalítico y la alimentación de nuevo aporte en la corriente o zona de reacción de al menos un reactor, comprendiendo la composición etileno interpolimerizado con al menos un comonómero insaturado y caracterizada por tener:a) una relación de fluidez, I10/I2, desde 8 a 10,4, b) una M w /M n superior a 4 según se determina mediante cromatografía de permeabilización a través de gel, c) un índice de fluidez, I2, desde 0,1 a 10 gramos/10 minutos, d) una densidad de la composición inferior a 0,945 gramos/centímetro cúbico, y e) basado en el peso total de partes de polímero cristalizable, un porcentaje en peso a la temperatura máxima dominante por encima de 75°C, según se determina usando la técnica del fraccionamiento para el análisis de la cristalización en el intervalo de 20 a 100°C, igual a o superior al producto matemático de 1,7946 x 10' 28 x 10 (31 , 839 x densidad de la composición) con la densidad de la composición expresada en gramos/centímetro cúbico.
- 2Una composición de polímero que comprende etileno interpolimerizado con al menos un comonómero insaturado, en la que la composición se caracteriza por tener:a) una relación de fluidez, I10/I2, desde 8 a 10,4, b) una Mw/Mn superior a 4 según se determina mediante cromatografía de permeabilización a través de gel, c) un índice de fluidez, I2, desde 0,1 a 10 gramos/10 minutos, d) una densidad de la composición inferior a 0,945 gramos/centímetro cúbico, y e) basado en el peso total de partes de polímero cristalizable, un porcentaje en peso a la temperatura máxima dominante por encima de 75°C, según se determina usando la técnica del fraccionamiento para el análisis de la cristalización en el intervalo de 20 a 100°C, igual a o superior al producto matemático de 1,7946 x 10' 28 x 10 (31 , 839 x densidad de la composición) con la densidad de la composición expresada en gramos/centímetro cúbico.
- 3Un artículo fabricado que comprende la composición de interpolímero de etileno definida en la reivindicación 2.
- 4El artículo fabricado de acuerdo con la reivindicación 3, en el que el artículo es una película, capa de película, revestimiento, pieza moldeada, bolsa, saco, parche o lámina.
- 5El artículo fabricado de acuerdo con la reivindicación 4, en el que la película es una película monocapa.
- 6El artículo fabricado de acuerdo con la reivindicación 4, en el que la película es una película multicapa.
- 7El artículo fabricado de acuerdo con la reivindicación 4, en el que la película es una película soplada.
- 8La composición de acuerdo con la reivindicación 1, en la que el al menos un comonómero insaturado es una α-olefina seleccionada del grupo que consiste en propileno, 1-buteno, 1-isobutileno, 1-hexeno, 4-metil-1-penteno, 1-penteno, 1-hepteno y 1-octeno.
- 9La composición de acuerdo con la reivindicación 1, en la que el al menos un comonómero insaturado es una α-olefina C3-C20.
- 10La composición de acuerdo con la reivindicación 1, en la que el interpolímero es un copolímero de etileno y 1-octeno.
- 11El procedimiento de acuerdo con la reivindicación 1, en el que uno de los al menos dos reactores es un reactor de circuito cerrado de recirculación. ES 2 178 232 T5
- 12El procedimiento de acuerdo con la reivindicación 1, en el que los al menos dos reactores son reactores de circuito cerrado de recirculación.
- 13El procedimiento de acuerdo con la reivindicación 1, en el que el procedimiento se opera no adiabáticamente.
- 14El procedimiento de acuerdo con la reivindicación 13, en el que el sistema comprende además al menos un aparato de intercambio de calor que separa el calor de reacción o de polimerización de la corriente de reacción del procedimiento a una intensidad de al menos 7,4 kW/m 3 -°K.
- 15El procedimiento de acuerdo con la reivindicación 1, en el que la inyección separada proporciona un retraso en la puesta en contacto y mezcla entre el catalizador inyectado y la alimentación de nuevo aporte inyectada de al menos 2 segundos.
- 16El procedimiento de acuerdo con la reivindicación 1, en el que se emplean mezcladores estáticos en los puntos de inyección de la alimentación de nuevo aporte.
- 17El procedimiento de acuerdo con la reivindicación 1, en el que se emplean mezcladores estáticos en los puntos de inyección del catalizador y de la alimentación de nuevo aporte.
- 18El procedimiento de acuerdo con la reivindicación 1, en el que el sistema comprende además al menos dos puntos de inyección de alimentación de nuevo aporte.
- 19El procedimiento de acuerdo con la reivindicación 1, en el que el comonómero de nuevo aporte se inyecta en el primer reactor.
Independent claims19
1,038 paragraphs in 153 sections, as filed
IS 2 178 232 T5
DESCRIPTION
Ethylene interpolymer compositions of wide distribution of molecular weights and uniform composition, process for their manufacture and articles produced with them
This invention relates to an ethylene interpolymer composition characterized by having a broad molecular weight distribution (MWD) and improved compositional uniformity. The invention also relates to a process for preparing such a composition and to manufactured articles prepared from the new composition. The new composition exhibits good processibility and improved toughness properties, especially excellent impact and tear resistance to the film, and is particularly well suited for use in applications such as high performance garbage container liners and garbage bags. transportation of heavy loads.
In the manufacture of ethylene interpolymers such as ethylene interpolymerized with at least one unsaturated comonomer, a number of polymerization methods and procedures are known. For example, single-site, constrained geometry catalyst systems have been described for the manufacture of olefin polymers with high compositional uniformity and relatively narrow molecular weight distributions.
Variations in the reactor systems used for the manufacture of ethylene interpolymers are also known. For example, on the one hand, single-site catalyst systems are described to provide narrow MWD products of uniform composition (for example, the EXACT plastomers commercially supplied by Exxon Chemical Corporation) when used in a high pressure polymerization system and vice versa. products with decreased homogeneity with respect to short chain branching distribution and broader molecular weight distribution (e.g. EXCEED resins commercially available from Exxon Chemical Corporation) when used in a low pressure gas phase polymerization process.
While the art is replete with various products and manufacturing techniques, the known range of manufacturability still does not allow the manufacture of ethylene interpolymer compositions characterized by good processability and excellent toughness properties such as excellent impact resistance. and the tear of the film. That is, known ethylene interpolymer compositions (either as single-reactor products, multi-reactor products, or polymer blends) do not exhibit the desired balance of good processability (i.e., sufficient extrusion processing characteristics to avoid, for example melt fracture which gives rise to objections during manufacture of blown film with sufficient melt strength to allow for example good stability to the formation of bubbles to maximize productivity) and excellent toughness.
Traditional polyethylene dissolution to achieve improved toughness properties involves manufacturing products with narrow molecular weight distributions as broad molecular weight distributions are known to produce reduced toughness properties. Beyond providing a narrow molecular weight distribution, linear polyethylenes are known to provide improved toughness properties relative to highly branched LDPE (low density polyethylene). Beyond a narrow molecular weight distribution and linear polymer backbone, compositional uniformity has been offered to achieve improved toughness properties. However, while the combination of a narrow molecular weight distribution, a linear polymer backbone, and compositional uniformity can provide improved toughness, this combination of polymer properties invariably provides poor processability (e.g., occurrence of melt fracture).
In contrast to the combination of narrow molecular weight distribution, increased compositional uniformity, and linear polymer backbone, to achieve the balance of good workability (i.e., melt fracture strength and bulk strength cast) and toughness properties, Lai et al. describe in US Pat. No. 5,272,236, substantially linear ethylene polymers characterized by having a narrow molecular weight distribution, high compositional uniformity, and long chain branching.
Other solutions proposed to achieve the desired balance of properties include polymer blends such as those described by Kale et al. In US Patent Number 5,210,142 and by Hazlitt et al. In US Patent Number 5,370. 940. However, while such polymer blends exhibit good workability and workability properties, known polymer blends inevitably exhibit insufficient compositional uniformity to provide the desired toughness properties.
Since no known ethylene interpolymer composition provides the desired balance of good to excellent processability, melt fracture resistance, melt strength and toughness as demonstrated by high impact and tear strength, there is a need for an improved ethylene interpolymer composition. There is also a need for a
ES 2 178 232 T5 process for the preparation of an improved ethylene interpolymer composition with the desired balance of properties. There is also a need for a process for the preparation of an improved ethylene interpolymer composition in which the process involves polymerization using multiple reactors and the process is characterized by improved flexibility such that a wide range of molecular weights and / or densities of the product. There is also a need for a blown film with good extrudability and high impact and tear resistance. These and other objects will become apparent from the detailed description of the present invention provided hereinbelow.
An ethylene interpolymer composition has been discovered which is characterized by a broad molecular weight distribution and which still also possesses a relatively high compositional uniformity with respect to its short chain branching distribution or its fractional crystallinity. One aspect of the invention is a process that is carried out in an ethylene polymerization system to prepare an ethylene polymer composition, the system comprising at least two injection points and at least two polymerization reactors, each reactor having a reaction stream or zone in which at least one catalytic system and the fresh feed are injected and in which the fresh feed comprises ethylene and optionally at least one unsaturated comonomer, the process comprising operation in continuity of at least two polymerization reactors and separately injecting the catalytic system and the fresh feed into the stream or reaction zone of at least one reactor, the composition comprising ethylene interpolymerized with at least one unsaturated comonomer and characterized by having:
a) a fluidity relationship, I<sub>10</sub>/ I<sub>2</sub>, from 8 to 10.4,
b) a Mw / Mn greater than 4 as determined by gel permeation chromatography,
c) a melt index, I2, from 0.1 to 10 grams / 10 minutes,
d) a density of the composition of less than 0.945 grams / cubic centimeter, and
e) based on the total weight of parts of crystallizable polymer, a weight percentage at the dominant maximum temperature above 75 ° C, as determined using the fractionation technique for analysis of crystallization in the range of 20 to 100 ° C, equal to or greater than the mathematical product of 1.7946 x 10 '<sup>28</sup> x 10<sup>(31.839 x composition density)</sup> with the density of the composition expressed in grams / cubic centimeter.
A second aspect of the invention is a polymer composition comprising ethylene interpolymerized with at least one unsaturated comonomer, in which the composition is characterized by having:
a) a fluidity ratio, I10 / I2, from 8 to 10.4,
b) a Mw / Mn greater than 4 as determined by gel permeation chromatography,
c) a flow rate, I<sub>2</sub>, from 0.1 to 10 grams / 10 minutes,
d) a density of the composition of less than 0.945 grams / cubic centimeter, and
e) based on the total weight of parts of crystallizable polymer, a weight percentage at the dominant maximum temperature above 75 ° C, as determined using the fractionation technique for analysis of crystallization in the range of 20 to 100 ° C, equal to or greater than the mathematical product of 1.7946 x 10 '<sup>28</sup> x 10<sup>(31</sup>,<sup>839 x composition density)</sup> with the density of the composition expressed in grams / cubic centimeter.
The third aspect of the invention is a manufactured article comprising an ethylene interpolymer composition, the composition comprising ethylene interpolymerized with at least one unsaturated comonomer and characterized by having:
a) a fluidity relationship, I<sub>10</sub>/ I<sub>2</sub>, from 8 to 10.4,
b) a Mw / Mn greater than 4 as determined by gel permeation chromatography,
c) a melt index, I2, greater than 0.1 grams / 10 minutes,
d) a density of the composition of less than 0.945 grams / cubic centimeter, and
e) based on the total weight of crystallizable polymer parts, a weight percent at the dominant maximum temperature above 75 ° C, as determined using the fractionation technique
ES 2 178 232 T5 for the analysis of crystallization in the range from 20 to 100 ° C, equal to or greater than the mathematical product of 1.7946 x 10<sup>-28</sup> x 10<sup>(31.839 x composition density)</sup> with the density of the composition expressed in grams / cubic centimeter.
In general, the invention represents the ability to separate I10 / I2, MWD and composition uniformity into substantially independent properties and achieve a previously unknown combination of these intrinsic properties as well as a previously unknown combination of performance properties.
Figure 1 is a graph of weight percent crystallized at the dominant maximum temperature above 75 ° C, determined using a fractionation technique for analysis of crystallization (i.e., CRYSTAF ™ fractional separation kit, computer program, and procedures as provided by PolymerChar) in the range of 20 to 100 ° C and based on the total amount of parts of crystallizable polymer, for compositions of the invention and comparative compositions as a function of the density of the composition.
Figure 2 is a CRYSTAF curve for composition 1 of the invention including the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 3 is a CRYSTAF curve for composition 2 of the invention including the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 4 is a CRYSTAF curve for comparative composition 3 including the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 5 is a CRYSTAF curve for comparative composition 4 including maximum temperature assignments and weight fraction integration for areas corresponding to the respective maximum temperatures.
Figure 6 is a CRYSTAF curve for comparative composition 5 including maximum temperature assignments and weight fraction integration for the areas corresponding to the respective maximum temperatures.
Figure 7 is a CRYSTAF curve for comparative composition 6 including maximum temperature assignments and weight fraction integration for areas corresponding to the respective maximum temperatures.
Figure 8 is the CRYSTAF curve for composition 7 of the invention including the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 9 is the CRYSTAF curve for composition 8 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 10 is a CRYSTAF curve for composition 9 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 11 is a CRYSTAF curve for composition 10 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 12 is a low shear rheology curve of compositions 1 and 2 of the invention and comparative compositions 3 and 4.
Figure 13 is an ATREF-DV curve comparing the distribution of short chain branching as related to the viscometrically determined average molecular weight (Mv) of composition 1 of the invention and comparative composition 3.
Figure 14 is an ATREF-DV curve comparing the distribution of short chain branching as related to the viscometrically determined average molecular weight (Mv) of composition 2 of the invention and comparative composition 3.
IS 2 178 232 T5
Figure 15 is an ATREF-DV curve comparing the distribution of short chain branching as related to viscometrically determined average molecular weight (M<sub>v</sub>) of compositions 1 and 2 of the invention.
Figure 16 is an ATREF-DV curve comparing the distribution of the short chain branching as it relates to the viscometrically determined average molecular weight (Mv) of composition 2 of the invention and comparative composition 4.
Figure 17 is a comparison of the gel permeabilization chromatography (GPC) curves of composition 2 of the invention and comparative composition 3.
Figure 18 is a comparison of the gel permeabilization chromatography (GPC) curves of composition 1 of the invention and comparative composition 3.
Figure 19 is a comparison of gel permeation chromatography (GPC) curves of compositions 1 and 2 of the invention.
Figure 20 is a comparison of the gel permeation chromatography (GPC) curves of composition 2 of the invention and comparative composition 4.
Figure 21 is a comparison of the molecular weight determined by GPC versus the relative weight fraction of composition 1 of the invention and comparative composition 3.
Figure 22 is a comparison of the high molecular weight determined by GPC (up to 5,500,000 g / mole) and the weight fraction of compositions 1 and 2 of the invention and comparative composition 3.
Figure 23 is a comparison of the high molecular weight determined by GPC (up to 1,500,000 g / mole) and the weight fraction of compositions 1 and 2 of the invention and comparative composition 3.
Figure 24 is a graph of blown film tear strength as a function of weight percent of crystallized polymer portion at the dominant maximum temperature above 75 ° C for compositions 1 and 2 of the invention and comparative compositions 3 and 4.
Figure 25 is the CRYSTAF curve for composition 11 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 26 is a process flow diagram of one of the two reactors used for the manufacture of composition 9 of the invention illustrating the simultaneous injection and mixing of the catalyst and the fresh feed using a mechanical mixer.
Figure 27 is a process flow diagram of one of the two reactors used for the manufacture of compositions 1, 2, 7, 8 and 10-15 of the invention illustrating separate injection and mixing of catalyst and feed again contribute using static mixers.
Figure 28 is a CRYSTAF curve for composition 12 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 29 is a CRYSTAF curve for composition 16 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 30 is a CRYSTAF curve for composition 17 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 31 is a CRYSTAF curve for composition 18 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
Figure 32 is a CRYSTAF curve for composition 19 of the invention including maximum temperature assignments and weight fraction integration for areas corresponding to respective maximum temperatures.
As mentioned above, Figure 1 is a graph of the weight percent crystallized (based on the total amount of parts of crystallizable polymer) at the dominant maximum temperature above 75 ° C as a function of the density of the composition. The percentage by weight crystallized at the dominant maximum temperature was determined by the fractionation technique for the analysis of crystallization in the range of
ES 2 178 232 T5 at 100 ° C. Compared to comparative compositions, Figure 1 indicates that a composition of the present invention has a higher amount of polymer parts of higher crystallization at equivalent compositional densities. Such increases in polymer portions of higher crystallization result in improved composition uniformity with respect to the distribution of short chain branching or fractional crystallization of the new composition.
While the CRYSTAF curve for a composition of the invention indicates improved compositional uniformity, especially at higher overall composition densities, the CRYSTAF curves for known compositions show at least two distinct polymer parts. For example, as illustrated in Figure 8 for composition 7 of the invention, at a density of approximately 0.917 g / cm<sup>3</sup>, a composition of the invention exhibits a broad smooth polymer part and a pronounced polymer part. Additionally, Figures 2 and 3 illustrate, at a density of approximately 0.927 g / cm<sup>3</sup> (i.e. compositions 1 and 2 of the invention), the CRYSTAF curve of a composition of the invention will essentially reflect a pronounced polymer part with a plateau that occurs at a lower maximum temperature than that corresponding to the pronounced polymer part .
Conversely, the CRYSTAF curve of a conventional heterogeneously branched ethylene polymer (Figure 6), such as DOWLEX ™ 2045 LLDPE (linear low-density polyethylene) resin, an ethylene / 1-octene copolymer of density 0.920 g / cm<sup>3</sup> and a melt index I2 of 1.0 supplied by The Dow Chemical Company, it shows two highly differentiated pronounced polymer parts.
Substantial distinction between the dominant polymer portions of an ethylene interpolymer composition has been found to result in reduced tear properties when the composition is made into a film. In particular, it was surprisingly found that a composition having a broad molecular weight distribution to achieve good treatability can be manufactured with optimized compositional uniformity and thus ensure that manufactured articles prepared therefrom will exhibit a improved toughness.
The term "dominant maximum temperature" as used herein refers to the maximum temperature as determined from the fractionation technique for analysis of crystallization in the range of 20 to 100 ° C which represents and corresponds to the percentage by weight the highest part of crystallized polymer based on the total amount of crystallizable polymer parts for the entire composition. Each composition with crystallizable polymer parts will have only one dominant maximum temperature although the composition can be characterized as having crystallized polymer parts measurable at several different maximum temperatures. When a composition has more than one maximum temperature that represents and corresponds to the highest percentage by weight of crystallized polymer parts, the dominant maximum temperature will be that maximum temperature that occurs at the lowest temperature. For example, for a composition characterized by having a 40 weight percent crystallized polymer portion that occurs at two different maximum temperatures, 80 ° C and 99 ° C, and in which all other maximum temperatures represent and correspond to lower weight percentages of crystallized polymer parts of the composition, the dominant maximum temperature will be 80 ° C (i.e. the lowest of 80 ° C and 99 ° C) and the percentage by weight of the part of polymer crystallized at the dominant maximum temperature will be 40 percent by weight.
The term "composition density" as used herein means the density of a single component polymer or a polymer blend of at least two ethylene polymers measured in accordance with ASTM D-792. The term "composition density" refers to a measure of the solid state density of granules, film or a molding as distinguished from a determination of melt density.
The term "polymer", as used herein, refers to a polymeric compound prepared by polymerizing monomers, either of the same or a different type. The generic term "polymer" thus encompasses the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer".
The term "interpolymer", as used herein, refers to polymers prepared by polymerizing at least two different types of monomers. The generic term "interpolymer" thus includes the term "copolymers" (which is usually used to refer to polymers prepared from two different monomers) as well as the term "terpolymers" (which is usually used to refer to polymers prepared from three different types of monomers).
The term "heterogeneously branched linear ethylene polymer" is used herein in the conventional sense in reference to a linear ethylene interpolymer having a comparatively low short chain branching distribution index. That is, the interpolymer has a relatively broad short chain branch distribution. Heterogeneously branched linear ethylene polymers have a SCBDI (short chain branching distribution index) of less than 50 percent and more typically less than 30 percent.
The term "homogeneously branched linear ethylene polymer" is used herein in the conventional sense to refer to a linear ethylene interpolymer in which the comonomer is randomly distributed within
ES 2 178 232 T5 of a given polymer molecule and wherein substantially all polymer molecules have the same ethylene to comonomer molar ratio. The term refers to an ethylene interpolymer that is characterized by a relatively high short chain branching distribution index (SCBDI) or composition distribution branching index (CDBI). That is, the interpolymer has an SCBDI greater than or equal to 50 percent, preferably greater than or equal to 70 percent, and more preferably greater than or equal to 90 percent. At higher degrees of compositional uniformity, homogeneously branched ethylene polymers can be further characterized as essentially lacking a measurable high-density, high-crystallinity polymer portion as determined using a temperature-increasing elution fractionation technique. (abbreviated here as "TREF").
The SCBDI is defined as the percentage by weight of polymer molecules that have a comonomer content within 50 percent of the median total molar comonomer content and represents a comparison of the distribution of the monomer in the interpolymer with the distribution of the expected monomer for a Bernoulli type distribution. The SCBDI of an interpolymer can be easily calculated from the TREF as described, for example, by Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Volume 20, page 441 (1982), or in US Patents 4,798,081; 5,008,204; or by LD Cady, "The Role of Comonomer Type and Distribution in LLDPE Product Performance," SPE Regional Technical Conference, Quaker Square Hilton, Akron, Ohio, October 1-2, pages 107-119 (1985), descriptions of all of which are incorporated herein by reference. However, the preferred TREF technique does not include purge amounts in the SCBDI calculations. More preferably, the monomer distribution of the interpolymer and the SCBDI are determined using NMR (nuclear magnetic resonance) analysis. <sup>13</sup>C according to the techniques described in US Patent Number 5,292,845; US Patent Number 4,798,081; US Patent Number 5,089,321 and by JC Randall in Rev. Macromol. Chem. Phys., C29, pages 201-317, the descriptions of both of which are incorporated herein by reference.
In analytical temperature rise elution fractionation analysis (as described in US Patent Number 5,008,204 and abbreviated herein as "ATREF"), the film or composition to be analyzed is dissolved in a solvent. suitable hot (eg, trichlorobenzene) and allowed to crystallize in a column containing an inert support by slowly reducing the temperature. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene). The ATREF curve is also often referred to as the short chain branching distribution (SCBD), as it indicates how the comonomer (e.g. octene) is uniformly distributed throughout the sample because as the elution temperature decreases, increases comonomer content.
Short chain branching distribution and other compositional information can also be determined using the fractionation technique for crystallization analysis such as the CRYSTAF fractionation separation package commercially available from PolymerChar, Valencia, Spain. Those skilled in the art will appreciate that the CRYSTAF fractionation separation technique is more convenient than the TREF techniques. The CRYSTAF fractionation separation unit consists of five (5) stainless steel vessels, each with a volume of 60 milliliters, installed in an HP5800 II gas chromatograph oven. An optical-electronic underdetector is used to measure the concentration of polymer in the solution that remains at each sampling stage during the crystallization process. Reagent grade 1,2,4-trichlorobenzene is used as the solvent. A Hamilton dispenser is programmed to fill the vessels with solvent and sample the reactor-reactors to determine the polymer concentration.
Fractional separation begins with the addition of 21 milligrams of polymer composition to 30 milliliters of 1,2,4-trichlorobenzene (0.07% w / w). The dissolution step is carried out at 140 ° C for 45 minutes. After dissolution, the temperature of the solution is lowered to 100 ° C at a rate of 40 ° C / minute and allowed to stand at 100 ° C for 30 minutes to equilibrate. The detector is set to zero reading with pure 1,2,4-trichlorobenzene and crystallization is initiated by establishing a cooling rate of 0.3 ° C / minute to 30 ° C. For compositions having densities less than 0.89 g / cm<sup>3</sup>Cryogenic CO 2 cooling at 20 ° C is typically required to quantify the entire range of crystallizable polymer parts.
At regular intervals during crystallization, 1.3 milliliters of the filtered solution is automatically transported from the dispenser to the detector. The detector reading is averaged over 10 seconds and 0.8 milliliters of solution is returned to the container. The transport line between the vessel and the detector is purged with 2 milliliters of pure 1,2,4-trichlorobenzene which is removed for disposal. The sampling sequence is repeated until 32 detector data points are obtained for each vessel over the entire crystallization temperature range. At the end of the sampling sequence or program, additional measurements are made in order to measure the soluble fraction of the polymer composition.
Once the analysis is complete, the temperature of each of the vessels is increased to 140 ° C in order to re-dissolve any polymer that remains on the filter. The vessels are emptied and cleaned with 35 milliliters of pure 1,2,4-trichlorobenzene at 140 ° C. The first derivative of the concentration versus temperature curve obtained is taken as the distribution of the short chain branching of the composition of
ES 2 178 232 T5 polymer. The specific integration of the areas under the peak temperatures can quantify the amount of crystallizable polymer parts associated with the specific peak temperatures. The maximum temperature which is a temperature at which a significant amount of polymer crystallizes to the extent of a "maximum" is illustrated by the derivative of the concentration vs. temperature curve.
Those skilled in the art will appreciate that the level of precision for CRYSTAF fractionation separation is typically very high. That is, the weight percent determination at the dominant maximum temperature above 75 ° C is reproducible within ± 2 percentage points or ± less than 5% under PolymerChar recommended standard methods and procedures. Additional details regarding the fractionation technique for crystallization analysis are provided by Benjamin Monrabal in "Crystallization Analysis Fraction: A New Technique for the Analysis of Branching Distribution in Polyolefins", Journal of Applied Polymer Science, Volume 52, pp. 491-499 (1994), the description of which is incorporated herein by reference.
Based on the total weight of crystallizable polymer parts, the new composition is generally characterized as having a weight percent at the dominant maximum temperature above 75 ° C, as determined using the fractionation technique for analysis of crystallization in the . 20 to 100 ° C range, equal to or greater than the mathematical product of 1.7946 x 10<sup>-28</sup> x io<sup>(31.839 x density of the c</sup>°<sup>mp</sup>°<sup>sition)</sup> with the density of the composition expressed in grams / cubic centimeter, preferably equal to or greater than the mathematical product of 1.7946 x 10<sup>-28</sup> x 10<sup>(31.839 x density of the c</sup>°<sup>mp</sup>°<sup>sition)</sup> with the density of the composition expressed in grams / cubic centimeter and less than or equal to 90, and more preferably equal to or greater than the mathematical product of 1.7946 x 10<sup>-28</sup> x 10<sup>(31,839</sup> x <sup>d</sup>ens<sup>go</sup>to<sup>d</sup> of <sup>to</sup> composition) with the density of the composition expressed in grams / cubic centimeter and less than or equal to 80.
Also, as indicated in Figure 1, the composition of the invention can generally be characterized as having a percentage by weight of part of polymer crystallized at the dominant maximum temperature above 75 ° C, as determined using a fractionation technique. for analysis of crystallization in the range 20 to 100 ° C, this is at least 10 percent, preferably at least 30 percent and more preferably at least 40 percent higher than the percentage by weight of part of polymer crystallized at the dominant maximum temperature above 75 ° C of a comparison composition having essentially the same I<sub>2</sub> and composition density.
By the phrase "essentially the same" is meant that the measured values for the I<sub>2</sub> of the composition of the invention and the comparison composition (not of the invention) are within 10 percent of each other and the measured values for the density of the composition of the composition of the invention and the comparison composition ( not of the invention) are within 0.3% of each other. Since the phrase is intended to establish an important requirement, compositions that do not fall within this requirement should not be compared for the purposes of determining relative crystallized fraction differences as defined in the present invention.
The term "comparison composition" refers to any composition that does not fully meet the defined requirements for the composition of the invention (although it may have essentially the same I2 and density of the composition as the composition of the invention) that is compared to the composition of the invention to determine the differences of relative crystallized fractions. Therefore, whether a composition is a composition of the invention or a comparison composition can be deduced from said comparative determinations.
The composition density of the new composition is less than 0.945 g / cm<sup>3</sup>, preferably less than 0.935 g / cm<sup>3</sup> and more preferably less than 0.93 g / cm<sup>3</sup>, and is generally in the range of 0.90 to 0.945 g / cm<sup>3</sup>, especially in the range from 0.91 to 0.935 g / cm<sup>3</sup> and most especially in the range from 0.915 to 0.93 g / cm<sup>3</sup> (as measured in accordance with ASTM D-792).
The molecular weight of polyolefin polymers is conveniently indicated using a melt index measure in accordance with ASTM D-1238, Condition 190 ° C / 2.16 kg (formerly known as "Condition E" and also known as I2). The melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear. The flow index I<sub>2</sub> Overall of the new composition is in the range from 0.1 to 10, more especially from 0.1 to 5 g / 10 minutes, and most especially in the range between 0.2 and 1.75 g / 10 minutes.
Other useful measures in characterizing the molecular weight of ethylene interpolymer compositions involve melt index determinations with higher weights, such as, for example, common ASTM D-1238, Condition 190 ° C / 10 kg (formerly known as "Condition N" and also known as I<sub>10</sub>). The ratio of a higher weight melt index determination to a lower weight determination is known as a melt flow ratio, and for the measured I10 and melt index I values<sub>2</sub> the melt flow ratio is conveniently designated I10 / I2. The new composition has a melt flow ratio I10 / I2 of from 8 to 10.4 and especially from 8.2 to 10.3 and more especially from 8.2 to 8.6.
IS 2 178 232 T5
The molecular weight distributions of the ethylene polymers are determined by gel permeation chromatography (GPC) on a Waters 150C elevated temperature chromatographic unit equipped with a differential refractometer and three mixed porosity columns. Columns are supplied by Polymer Laboratories and are commonly packed with pore sizes of 10<sup>3</sup>, 10<sup>4</sup>, 10<sup>5</sup> and 10<sup>6</sup> A. The solvent is 1,2,4-trichlorobenzene, from which 0.3 percent by weight solutions of the samples are prepared for injection. The flow rate is approximately 1.0 milliliters / minute, the unit operating temperature is approximately 140 ° C, and the injection size is 100 microliters.
Determination of molecular weight relative to polymer backbone is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes. Equivalent polyethylene molecular weights are determined using the appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Ward in Journal of Polymer Science, Polymer Letters, Volume 6, page 621, 1968) to obtain the following equation:
<sup>M</sup>polyethylene = <sup>a (M</sup>polystyrene<sup>)</sup> .
In this equation, a = 0.4316 and b = 1.0. The weight average molecular weight, Mw, is calculated in the usual way according to the following formula: Mj = (Σ w¡ (M<sup>j</sup>))<sup>j</sup>; where w, is the weight fraction of the molecules with molecular weight Mi that elute from the GPC column in the fraction i and j = 1 when Mw is calculated and j = -1 when Mn is calculated. The new composition has a Mw / Mn greater than or equal to 4, preferably greater than or equal to 4.5, and more preferably greater than or equal to 4.75, and especially in the range from 4 to 8 and most especially in the range from 4 to 7. However, when optimizing the I<sub>10</sub>/ I<sub>2</sub>, preferably M<sub>w</sub>/ M<sub>n</sub> It is in the range of 4 to 4.5.
Parallel plate rheology can be conveniently used to predict ease of extrusion processibility by indicating whether a particular ethylene interpolymer composition is shear thinned or not. In comparisons with known compositions having similar molecular weights and molecular weight distributions, Figure 12 indicates that the new composition has a highly favorable parallel plate rheology. The fabrication of the actual blown film confirms the favorable rheology of the new composition and also indicates that the new composition has relatively high strength at the onset of melt fracture and excellent melt strength. The excellent melt strength of the new composition results in excellent bubble formation stability during, for example, investigations for blown film fabrication.
Melt strength determinations are made at 190 ° C using a Goettfert Rheotens and an Instron capillary rheometer. The capillary rheometer is aligned and positioned above the Rheotens unit and supplies, at a constant piston speed of 25.4 mm / min, a fused polymer filament to the Rheotens unit. The Instron is equipped with a standard 2.1mm diameter 42mm length (L / D 20: 1) capillary nozzle and supplies the filament to the Rheotens unit take-up sprockets rotating at 10mm / s . The distance between the outlet of the Instron capillary nozzle and the point of narrowing on the Rheotens pick-up wheels was 100mm. The experiment to determine the melt strength begins by accelerating the take-up wheels on the Rheotens unit at 2.4 mm / s<sup>2</sup>, the Rheotens unit is capable of acceleration intensities from 0.12 to 120 mm / s<sup>2</sup>. As the speed of the Rheotens take-up wheels increases with time, the stretching force is recorded in centiNewtons (cN) using the Linear Variable Displacement Transducer (LVDT) on the Rheotens unit. The computerized data acquisition system of the Rheotens unit records the stretching force as a function of the speed of the take-up wheel. The actual value of the melt strength is taken from the stabilization period of the recorded stretching force.
The new composition can be formed by the method according to the claims. Any other convenient method may be considered, including dry blending of the selected polymer components together and subsequently melt blending the component polymers in a mixer or by blending the polymer components together directly in a mixer (for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder including a mixing extruder and a stirrer extruder employed directly downstream of a polymerization process).
Preferably, the novel composition is manufactured in-situ using any polymerization method and procedure known in the art (including solution, suspension or gas phase polymerization procedures at high or low pressures) provided that operations, reactor configurations, catalyst systems and the like are selected, employ and perform to truly provide the new composition with its defined combination of characteristics. A preferred method of manufacturing the new composition involves the use of a multiple reactor polymerization system with the various reactors operated in a series or parallel configuration or a combination of both when more than two reactors are employed. More preferably, the new composition is manufactured using a two reactor system in which the two reactors are operated in a series configuration. In a multi-reactor polymerization system (and especially in a two-reactor system) with reactors configured in series, the fraction of the polymer is
ES 2 178 232 T5 generally from 5 to 60 percent by weight, preferably from 10 to 40 percent by weight, and more preferably from 15 to 35 percent by weight in the first reactor. In particularly preferred embodiments of the invention, the fraction of the polymer in the first reactor will be less than 36 percent by weight, especially less than 31 percent by weight, and most especially less than or equal to 27 percent by weight. The first reactor is a multiple reactor configuration (for example reactors arranged in series) which will typically be that reactor located farthest from the product outlet for finishing operations. The serial configuration of at least two polymerization reactors is preferred in the present invention.
Also, in a preferred embodiment of the invention, a polymerization system consisting of at least one recirculating flow closed loop reactor and especially a polymerization system consisting of at least two non-operated recirculating closed loop reactors is used. adiabatically to make the new composition. Such preferred polymerization systems are as described by Kao et al. In copending patent application number 08/831172, filed April 1, 1997, the disclosure of which is incorporated herein by reference.
Non-adiabatic polymerization is preferably achieved at a volumetric thermal separation rate equal to or greater than 7.4 kW / m<sup>3</sup>- ° K, more preferably equal to or greater than 11.1 kw / m<sup>3</sup>- ° K, more especially equal to or greater than 22.2 kw / m<sup>3</sup>° K and most especially equal to or greater than 37 kw / m<sup>3</sup>° K.
The expression "volumetric thermal separation rate" as used herein is the process heat transfer coefficient, U, in kW / square meter- ° K, multiplied by the heat exchange area, A, in square meters, of the apparatus. of heat exchange divided by the total volume of the reactor system, in cubic meters. A moderately skilled person will recognize that there must be consistency as to whether the interior or exterior parameters of the procedure are used in calculations and determinations of U and surface area. The calculations contained here are based on the outer surface areas and outer diameters of heat exchange tubes, coils, etc. and the reactor mixture flows through said tubes, coils, etc. or not.
To effect non-adiabatic polymerization, any suitable heat exchange apparatus, in any configuration, can be used, including, for example, a cooling coil placed in a polymerization reactor (s), a shell-and-tube type heat exchanger placed in a polymerization reactor or reactors in which the flow stream (s) from the reactor (also referred to in the art as "reaction mixture") passes through the tubes, or an entire recirculating flow closed loop reactor that is designed as a heat exchange apparatus by providing cooling via a jacket or double tubing. In a suitable design, a form of a shell and tube type heat exchanger may be used in which the shell of the exchanger has an inlet and outlet for the reactor flow stream and an inlet and outlet for the transfer medium. thermal (eg water, water / glycol, steam, SYLTHERMO ™ material or media supplied by The Dow Chemical Company under the designation DOWTHERM®). In another design, the flow stream from the reactor flows through a plurality of heat transfer tubes within the heat exchanger shell while the heat transfer medium flows over the outer surfaces of the tubes that transfer heat from reaction or polymerization from the reactor flow stream. Alternatively, the reaction stream flows through the shell and the heat transfer medium flows through the tubes. Suitable heat exchange apparatuses for use in the manufacture of the new composition are commercially available items (such as, for example, a static mixer / heat exchanger supplied by Koch) that have a tortuous path entirely defined by the tubular walls. of the tubes and / or having solid static inner elements that form an inner band through which the reaction mixture flows.
It is generally contemplated that any known catalyst system useful for olefin polymerization can be used to make the new composition including the conventional Ziegler-Natta type catalyst systems, chromium catalyst systems, the so-called single-site catalyst systems described, for example, Monocyclopentadienyl transition metal olefin polymerization catalysts disclosed by Canich in US Pat. 5,026,798 or by Canich in U.S. Patent 5,055,438, the disclosures of which are incorporated herein by reference) and constrained geometry catalyst systems (for example, as described by Stevens et al. In the Patent US 5,064,802, the disclosure of which is incorporated herein by reference). However, in preferred embodiments, a conventional Ziegler-Natta type catalyst system is used to make the new composition. For preferred embodiments using a polymerization system consisting of at least two reactors, a conventional Ziegler-Natta type catalyst system is preferably employed in each of the at least two reactors.
The preferred Ziegler-Natta catalysts for use in making the new composition are those that are useful at relatively high polymerization temperatures. Examples of said compositions are those obtained from organic magnesium compounds, alkyl halides or aluminum halides or hydrogen chloride, and a transition metal compound. Examples of such catalysts are described in US Patent Nos.<sup>s</sup> 4,314,912 (Lowery, Jr et al.), 4,547,473 (Glass et al.), And 4,612,300 (Coleman, III), the descriptions of which are incorporated herein by reference.
IS 2 178 232 T5
Particularly suitable organic magnesium compounds include, for example, hydrocarbon soluble dihydrocarbylmagnesiums such as dialkyl magnesiums and diaryl magnesiums. Examples of suitable dialkyl magnesium include particularly n-butyl-sec-butyl-magnesium, di-isopropyl-magnesium, di-n-hexylmagnesium, iso-propyl-n-butyl-magnesium, ethyl-n-hexyl-magnesium, ethyl-n- bu-tyl-magnesium, di-n-octyl-magnesium, and others in which the alkyl has from 1 to 20 carbon atoms. Examples of suitable diaryl magnesium include diphenyl magnesium, dibenzyl magnesium, and ditolyl magnesium. Suitable organic magnesium compounds include alkyl and aryl magnesium alkoxides and aryl oxides and aryl and alkyl magnesium halides with halogen-free organic magnesium compounds being the most desirable.
Among the sources of halides that can be used herein are active non-metallic halides, metal halides, and hydrogen chloride.
Any method and procedure known in the art can be used to prepare a suitable Ziegler-Natta catalyst for use in the present invention. A suitable method and procedure is described in US Patent Number 4,612,300, the disclosure of which is incorporated herein by reference (Example P). The described method and procedure involves sequentially adding to a volume of Isopar ™ E hydrocarbon, a suspension of anhydrous magnesium chloride in Isopar ™ hydrocarbon, a solution of EtAlCb in n-hexane, and a solution of Ti (O-iPr) 4 in Isopar ™ hydrocarbon, to produce a suspension containing a magnesium concentration of 0.166 M and a Mg / Al / Ti ratio of 20.0: 12.5: 3.0. An aliquot of this suspension and a dilute Et3Al (TEA) solution are pumped independently in two separate streams and combined immediately prior to introduction into the polymerization reactor system to give an active catalyst with a final molar ratio of TEA: 6.2: 1 Ti.
Suitable unsaturated comonomers useful for polymerization with ethylene include, for example, ethylenically unsaturated monomers, conjugated or unconjugated dienes, polyenes, etc. Examples of such monomers include C3-C20 α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1pentene, 1-heptene, 1-octene, 1-nonene, 1-decene , and the like. Preferred comonomers include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene, and 1-octene is especially preferred. Other suitable monomers include styrene, halogen or alkyl substituted styrenes, tetra-fluoroethylene, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and cycloalkenes, eg, cyclopentene, cyclohexene, and cyclooctene.
Additives, such as antioxidants (e.g. hindered phenolic compounds) such as IRGANOX ™ 1010 or IRGANOX ™ 1075 supplied by Ciba Geigy, phosphites (e.g. IRGaFoS ™ 168 also supplied by Ciba Geigy, adhesion additives (e.g. PIB), SaNdOSTAB PEPQ ™ (supplied by Sandoz), pigments, colorants, fillers, antistatic agents, Processing aids and the like can also be included in the new composition of manufactured articles. Although not generally required, films, coatings, and molded articles formed from the new composition may also contain additives to improve antistick, mold release characteristics, and coefficient of friction including, but not limited to, treated silicon dioxide and untreated, talc, calcium carbonate, and clay, as well as primary, secondary, and substituted fatty acid amides, release agents, silicone liners, etc. Still other additives, such as quaternary ammonium compounds alone or in combination with ethylene-acrylic acid copolymers (EAA) or other functional polymers, can also be added to improve the antistatic characteristics of films, coatings and molded articles formed from the new composition and allow the use of the composition in, for example, high-strength packaging of electronically sensitive items.
The fabricated articles of the invention (such as, for example, but not limited to, films, film coating, fibers, molded articles, and coatings) may further include recycle and waste materials and diluent polymers, as long as they are maintained. Balanced properties of processability, impact resistance and tear resistance. Examples of diluent materials include, for example, elastomers, rubbers and anhydride modified polyethylenes (for example LLDPE and HDPE grafted with polybutene and maleic anhydride) as well as high pressure polyethylenes such as, for example, low density polyethylene ( LDPE), ethylene / acrylic acid interpolymers (EAA), ethylene / vinyl acetate interpolymers (EVA), and ethylene / methyl methacrylate interpolymers (EMA), and combinations thereof.
The articles of manufacture of the invention may find utility in a variety of applications. Suitable applications are thought to include, for example, but are not limited to, monolayer films for packaging; multilayer packaging structures consisting of other materials such as, for example, biaxially oriented polypropylene or biaxially oriented ethylene polymer for shrink film and barrier shrink applications; containers and packagings formed via form / fill / seal machinery; peelable hermetically sealed container and packaging structures; containers for cooked food; compression filled containers; film for sealable stretch wrap packaging such as, for example, fresh produce packaging and market packaging for fresh red meat; liners and bags such as, for example, protective liner for cereals, bags for groceries / commercial items, and especially high-content sacks for transport and liners (bags) of high-performance garbage containers in which higher levels are now possible elevated
ES 2 178 232 T5 thickness reduction due to the improved toughness properties exhibited by the manufactured article of the invention.
The manufactured article of the invention can be prepared by any method known in the art. Suitable methods include, for example, lamination and coextrusion techniques or combinations thereof, blown film, cast film, extrusion coating, injection molding, blow molding, thermoforming, profile extrusion, pultrusion, compression molding, molding. rotational, or blow molding or injection operations or combinations thereof and the like.
The fabricated article of the invention can be of any thickness required or desired for its end use application. In particular, the new film of the invention can be of any suitable film thickness, however, those skilled in the art will appreciate that a significant reduction in thickness may be possible due to the improved toughness properties exhibited by the new film.
Examples
The following examples are provided for the purpose of explanation rather than limitation.
In an evaluation to investigate the tear strength of various ethylene interpolymer compositions, various compositions were obtained. For this investigation, Comparative Composition 1 and Composition 2 were manufactured using a non-adiabatic polymerization system consisting of two recirculating closed-loop reactors configured in series. The process conditions used in the manufacture of the two examples of the invention are provided in Table 1.
Also for research, Comparative Composition 3 was manufactured according to the methods and procedures described in US Patent Number 5,370,940 using an adiabatic polymerization system consisting of two spherical reactors configured in series. The process conditions employed in the manufacture of comparative composition 3 are provided in Table 2.
Comparative Composition 4 was manufactured using the same polymerization system and process conditions similar to those employed in the manufacture of Comparative Compositions 1 and 2, except that a constrained geometry catalyst system was used in a closed flow loop Rx1 reactor. instead of a heterogeneous Ziegler-Natta type titanium coordination catalyst system.
IS 2 178 232 T5
Table 1
<td colspan="3">Comparative Example 1</td><td colspan="2">Invention Example 2</td>
<td></td><td>Rx1 closed-loop flow</td><td>Rx2 closed loop flow</td><td>Rx1 closed-loop flow</td><td>Rx2 closed loop flow</td>
<td>Process temperature, ° C</td><td> 161</td><td> 190</td><td> 161</td><td> 190</td>
<td>Procedure pressure, gauge kPa</td><td> 3620</td><td> 3620</td><td> 3620</td><td> 3620</td>
<td>Polymer concentration,% by weight</td><td> 10,6</td><td> 19,5</td><td> 10,6</td><td> 19,5</td>
<td>C2 conversion,% (global)</td><td> 73,6</td><td> 89,3 (92,4)</td><td> 73,5</td><td> 90 (92,9)</td>
<td>C2 solvent / feed ratio</td><td> 6,82</td><td> 2,80</td><td> 6,80</td><td> 2,80</td>
<td>C flow<sub>2</sub> (kg / h)</td><td> 40</td><td> 64</td><td> 40</td><td> 64</td>
<td>Ca flux of fresh input (kg / h)</td><td> 0</td><td> 8,6</td><td> 7,8</td><td> 0</td>
<td>Pure hydrogen flux, sccm (cm<sup>3 </sup>standard)</td><td> 1021</td><td> 3255</td><td> 950</td><td> 2968</td>
<td>Feed temperature, ° C</td><td> 40</td><td> 15</td><td> 40</td><td> 15</td>
<td>Recycling ratio</td><td> 17,7</td><td> 7,6</td><td> 17,7</td><td> 7,7</td>
<td>Polymer fraction,% by weight</td><td> 30,4</td><td> 69,6</td><td> 30,4</td><td> 69,6</td>
<td>Residence time, min</td><td> 20,6</td><td> 9,9</td><td> 20,6</td><td> 10</td>
Table 1 (Continuation)
<td colspan="3">Invention Example 1</td><td colspan="2">Invention Example 2</td>
<td></td><td>Rx1 closed-loop flow</td><td>Rx2 closed loop flow</td><td>Rx1 closed-loop flow</td><td>Rx2 closed loop flow</td>
<td>Catalyst type</td><td>Heterogeneous ZieglerNatta type titanium coordination catalytic system</td><td>Heterogeneous ZieglerNatta type titanium coordination catalytic system</td><td>Heterogeneous ZieglerNatta type titanium coordination catalytic system</td><td>Heterogeneous ZieglerNatta type titanium coordination catalytic system</td>
<td>Catalyst efficiency, Tm of product / kg of titanium</td><td> 1300</td><td> 490</td><td> 1400</td><td> 560</td>
<td>Volumetric thermal separation intensity (kW / m<sup>3</sup>. ° K)</td><td> 3 18,5</td><td> 11,5</td><td> 3 26</td><td> 10,8</td>
<td>Production rate, (kg / h) (Global)</td><td> 33</td><td> 76 (240)</td><td> 33</td><td> 75 (239)</td>
IS 2 178 232 T5
Table 2
<td colspan="3">Comparative Example 3</td>
<td></td><td>Spherical Rx1</td><td>Spherical Rx2</td>
<td>Process temperature, ° C</td><td> 159</td><td> 197</td>
<td>Polymer concentration,% by weight</td><td> 6,7</td><td> 12,2</td>
<td>C2 conversion,% (global)</td><td> 80</td><td> 90,5 (92,9)</td>
<td>C2 solvent / feed ratio</td><td> 13</td><td> 5,36</td>
<td>Solvent flow (kg / h)</td><td> 57,057</td><td> 52,716</td>
<td>C2 flow (kg / h)</td><td> 4389</td><td> 9854</td>
<td>C8 flow of fresh input (kg / h)</td><td> 1100</td><td></td>
<td>Pure hydrogen flux, sccm (cm<sup>3 </sup>standard)</td><td> 0</td><td> :700.000</td>
<td>Recycling ratio</td><td>Not available</td><td>Not available</td>
<td>Feed temperature, ° C</td><td> 76</td><td> 22</td>
<td>Polymer fraction,% by weight</td><td> 27,4</td><td> 72,6</td>
<td>Residence time, min</td><td>Not available</td><td>Not available</td>
Table 2 (Continuation)
<td colspan="3">Comparative Example 3</td>
<td></td><td>Spherical Rx1</td><td>Spherical Rx2</td>
<td>Catalyst type</td><td>Heterogeneous ZieglerNatta type titanium coordination catalytic system</td><td>Heterogeneous ZieglerNatta type titanium coordination catalytic system</td>
<td>Catalyst efficiency, Tm of product / kg of titanium (global)</td><td> 180</td><td></td>
<td>Volumetric thermal separation intensity (kW / m<sup>3</sup>. ° K)</td><td>Not available</td><td>Not available</td>
<td>Production rate, (kg / h) (Global)</td><td> 4136</td><td> 10956 (15092)</td>
IS 2 178 232 T5
With respect to the polymerization system used to make Comparative Composition 1 and Composition 2 of the invention, the two reactor system used to make Comparative Composition 3 requires significantly higher feed temperatures to avoid objectionable levels of gels in the product. finish. The independent control of polymer concentration and process temperature that is characteristic of non-adiabatic recirculating flow closed loop reactors proves to be of tremendous economic benefit with respect to the requirements for good gel quality, particularly at lower product flow rates.
The nominal 0.025 millimeter blown film was manufactured from compositions 1 and 2 of the invention and comparative compositions 3 and 4 on an Egan blown film manufacturing unit equipped with a 32: 1 L / D ratio extruder and 5.1 cm in diameter and a 7.6 cm annular nozzle. Blown film extrusion conditions for each film are provided in Table 3.
Table 3
<td>Example</td><td>Comparative Example 1</td><td>Example 2 of the invention</td><td>Comparative Example 3</td><td>Comparative Example 4</td>
<td>Nozzle clearance, mm</td><td> 0,89</td><td> 0,89</td><td> 0,89</td><td> 0,89</td>
<td>Melting temperature, ° C</td><td> 232</td><td> 229</td><td> 230</td><td> 228</td>
<td>Nozzle pressure</td><td> 4000</td><td> 4400</td><td> 4200</td><td> 3750</td>
<td>Production (kg / h)</td><td> 14</td><td> 13</td><td> 14</td><td> 8,5*</td>
<td>Height of crystallization line (cm)</td><td> 17,8</td><td> 17,8</td><td> 17,8</td><td> 25,4**</td>
<td>Spindle, rpm</td><td> 41</td><td> 41</td><td> 41</td><td> 25</td>
<td>Extruder amperage</td><td> 43</td><td> 44</td><td> 43</td><td> 39</td>
<td>Blowing ratio</td><td> 2,7</td><td> 2,7</td><td> 2,7</td><td> 2,7</td>
In actual blown film manufacture Comparative Composition 1 and Composition 2 of the invention and Comparative Composition 3 exhibited good processibility and excellent melt stability as indicated by relatively high production yields and heights of relatively low crystallization line (ie good bubble formation stability), respectively. Conversely, Comparative Composition 4 exhibited relatively low throughput and relatively high crystallization line height.
Table 4 lists some physical properties and performance properties of the film for Comparative Composition 1 and Composition 2 of the invention and Comparative Compositions 3 and 4.
Table 4 indicates that Comparative Composition 1 and Composition 2 of the invention have excellent tear resistance, good handling properties (ie, low film adhesion), and fairly wide molecular weight distributions. The tear strength of Comparative Composition 1 and Composition 2 of the invention was 33-46 percent and 34-37 percent, respectively, higher than the tear strength of Comparative Composition 4.
IS 2 178 232 T5
Table 4
<td>Example</td><td>Comparative Example 1</td><td>Example 2 of the invention</td><td>Comparative Example 3</td><td>Comparative Example 4</td>
<td>Composition density, g / cm<sup>3</sup></td><td> 0,9271</td><td> 0,9271</td><td> 0,9262</td><td> 0,9263</td>
<td>I2 g / 10 minutes</td><td> 0,44</td><td> 0,42</td><td> 0,55</td><td> 0,54</td>
<td>I10 g / 10 minutes</td><td> 4,51</td><td> 3,96</td><td> 5,01</td><td> 3,77</td>
<td>I10 / I2</td><td> 10,45</td><td> 9,47</td><td> 9,03</td><td> 6,98</td>
<td>Mw / M<sub>n</sub> via GPC</td><td> 4,74</td><td> 5,37</td><td> 5,53</td><td> 2,72</td>
<td>Weighted average molecular weight</td><td> 170700</td><td> 173000</td><td> 169300</td><td> 142000</td>
<td>Number average molecular weight</td><td> 36000</td><td> 32200</td><td> 30600</td><td> 52200</td>
<td>Rheotens melt strength, force in centiNewtons</td><td> 8,3</td><td> 9,45</td><td> 7,75</td><td> 7,3</td>
<td>Film adhesion, grams</td><td> 5,50</td><td> 5,72</td><td> 7,95</td><td> 6,40</td>
<td>Elmendorf medium type B CD</td><td> 526</td><td> 486</td><td> 573</td><td> 429</td>
<td>Elmendorf normalized, B CD</td><td> 591</td><td> 541</td><td> 556</td><td> 405</td>
<td>Elmendorf Standard Device B CD</td><td> 34</td><td> 65</td><td> 51</td><td> 47</td>
<td>Elmendorf Medium Type B MD</td><td> 490</td><td> 430</td><td> 477</td><td> 339</td>
<td>Elmendorf normalized B MD</td><td> 476</td><td> 494</td><td> 459</td><td> 369</td>
<td>Elmendorf standard device B MD</td><td> 78</td><td> 55</td><td> 35</td><td> 34</td>
Film adhesion was determined in accordance with ASTM D3354.
Elmendorf tear strength was determined in accordance with ASTM D1922 and normalization was at a thickness of 25mm.
In an investigation to determine the uniformity of the relative composition of various ethylene interpolymers, additional compositions were obtained and analyzed using the CRYSTAF fractional separation technique described above. Additional compositions for this investigation included comparative compositions 5 and 6 and 7-10.
Comparative Composition 5 was a linear low density polyethylene (LLDPE) resin supplied by The Dow Chemical Company under the trade designation LLDPE DOWLEX 2045 resin. Comparative Composition 6 was an experimental linear low density polyethylene (LLDPE) resin supplied by The Dow Chemical Company.
Comparative Compositions 7-10 were made using the same polymerization system described above as used to make Comparative Composition 1 and Composition 2 of the invention. The process conditions used for Comparative Compositions 7-10 were essentially similar to those employed for Comparative Composition 1 and Composition 2 of the invention except that the flux of fresh octene was higher for Comparative Compositions 7-10 and the hydrogen fluxes of fresh input to each reactor were adjusted to provide higher I10 / I2 ratios for the compositions
ES 2 178 232 T5 comparatives 7-10. Composition 7 of the invention was made using a 30 weight percent fraction of the polymer in the Rx1 reactor (ie, the first reactor). Comparative compositions 8-10 were made using a 25 weight percent polymer fraction in reactor Rx1.
The CRYSTAF curves (Figures 2-11) were generated for the various compositions and their respective weight percentages of part of the polymer crystallized at their respective dominant maximum temperatures above 75 ° C were derived from the CRYSTAF curves. Table 5 summarizes the physical properties and crystallization data for the various compositions.
Table 5
<td>Example</td><td>Density g / cm<sup>3</sup></td><td>I2, g / 10 min.</td><td>I10, g / 10 min.</td><td>I10 / I2</td><td>Mw / Mn</td><td>wt% crystallized at DPT (maximum dominant temperature) above 75 ° C</td>
<td>Comparative Example 1</td><td> 0,9271</td><td> 0,44</td><td> 4,61</td><td> 10,45</td><td> 4,74</td><td> 58,7</td>
<td>Example 2 of the invention</td><td> 0,9271</td><td> 0,42</td><td> 4,30</td><td> 10,25</td><td> 5,37</td><td> 95,7</td>
<td>Comparative Example 3</td><td> 0,9262</td><td> 0,55</td><td> 5,01</td><td> 9,03</td><td> 5,53</td><td> 53,0</td>
<td>Comparative Example 4</td><td> 0,9263</td><td> 0,54</td><td> 3,77</td><td> 6,98</td><td> 2,72</td><td> 40,8</td>
<td>Comparative Example 5</td><td> 0,920</td><td> 1,0</td><td>ND</td><td>ND</td><td>ND</td><td> 26,6</td>
<td>Comparative Example 6</td><td> 0,922</td><td> 0,50</td><td>ND</td><td>ND</td><td>ND</td><td> 29,6</td>
<td>Comparative Example 7</td><td> 0,917</td><td> 0,58</td><td> 6,84</td><td> 11,9</td><td> 6,42</td><td> 28,2</td>
<td>Comparative Example 8</td><td> 0,917</td><td> 0,64</td><td> 6,85</td><td> 10,7</td><td> 5,5</td><td> 31,2</td>
<td>Comparative Example 9</td><td> 0,917</td><td> 0,48</td><td> 5,0</td><td> 10,5</td><td> 5,69</td><td> 31,8</td>
<td>Comparative Example 10</td><td> 0,917</td><td>ND</td><td>ND</td><td>NA</td><td> 5,44</td><td> 31,8</td>
ND denotes "not determined".
NA denotes "not applicable".
Figure 1, which is a graph of the percentage by weight of the part of polymer crystallized at the dominant maximum temperature above 75 ° C as a function of the density of the composition for the compositions of the invention and the comparative compositions, is generated using the data in Table 5. Using the crystallization data for Comparative Composition 1 and Composition 2 of the invention and Comparative Compositions 3 and 4, Figure 24 was generated to illustrate the interrelationship between tear strength and weight percent of the crystallized polymer part. at the dominant maximum temperature above 75 ° C for the respective compositions. Figure 24 shows with respect to tear resistance performance that there is an apparent optimum at about 75 weight percent for the crystallized polymer portion at the dominant maximum temperature above 75 ° C.
ATREF was performed for comparative composition 1 and composition 2 of the invention and comparative compositions 3 and 4. Figures 13-16 provide various comparisons between the four compositions. In general, the various ATREF comparisons complement the CRYSTAF data by indicating that at equivalent overall compositional densities the compositions of the invention possess more polymer that crystallizes at higher temperatures, and this distinction becomes even more prominent at higher equivalent compositional densities. elevated. However, although their amount of polymer parts that crystallize at higher temperatures differ substantially, the compositions of the invention and the comparative compositions have essentially the equivalent molecular weight as indicated by the Mv results.
IS 2 178 232 T5
The raw molecular data obtained by GPC for Comparative Composition 1 and Composition 2 of the invention and Comparative Compositions 3 and 4 are provided in Table 6. Figures 17-23 are GPC comparisons between compositions of the invention and comparative compositions.
IS 2 178 232 T5
Table 6
<td rowspan="3">Comparative Example 4</td><td>E # g. f -g I% ω Q SJ_ φ Uí Q_ O CL <sup>7=5</sup> AND</td>
<td>B £ g. δ £ g -g ™ O ~ £ Z 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>i £ ° i 8 I a Q SJ_ φ Uí Q_ O CL <sup>73</sup> AND</td>
<td>φφ ^ Ε— B £ g. δ -g -g * oo o-2 cl φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>o O ° zs Φ <D 4; ñP Φ 2 i_ 2 ¡σ '2 -o CL Φ 05 or “Φ 70 O 0- <sup>73</sup> -g E</td>
<td>¿Φ gi φ φ a- Ε φ 2 2 ¡σ 'g. or -g ω α. φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>Í £ ot φ | I faith or Φ <sup>73</sup> Q_ O Q_ -o E</td>
<td><5 gi Φ φ> - Ε Φ ° L · - 2 ¡σ 'g_ or -g φ o ~ ο φ ° α- φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 Τ5
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<img file="ES2178232T5_D0005.tif" />
<img file="ES2178232T5_D0006.tif" />
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<img file="ES2178232T5_D0018.tif" />
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<img file="ES2178232T5_D0020.tif" />
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IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>i> = i sis Q S-1_ φ Q_ o CL <sup>73</sup> AND</td>
<td>δ<sub>φ1</sub>_Ε - ° or v. 2 £ g. or -gg% ω o ~ c cl O CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>i> = I? 8 ¡a Q s-l_ φ or Q_ O CL <sup>73</sup> AND</td>
<td>¿(0 ¿J φ φ s- E - θ o. E ΈΓ g. or -g φ £ φ Or "c <sup>or</sup> CL O CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>l O 1 φ φ him. 'ra' φ θ l. 2 ro 'g. cl φ<sub>ro</sub>or φ -z: ° or- <sup>73</sup> -g E</td>
<td>¿<5 ω i Φ Φ E Φ ° And i? g. or Q- ro ° ~ <sup>c</sup> ω g 0- Φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>E # g. f -g I | ® Q SJ_ φ Q_ O CL <sup>73</sup> AND</td>
<td>¿Φ ω i Φ 05 L. E Φ Φ ΙΕ ra 'g. o ω- ro ° ~ <sup>c</sup> Φ g 0- Φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
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<img file="ES2178232T5_D0036.tif" />
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<img file="ES2178232T5_D0041.tif" />
IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>u ° hs 1 Q SL φ O Q_ o CL <sup>7=5</sup> AND</td>
<td>φφ-Ε- ° ο ^ Β ΈΓ g. Ό £ φ% ω O ~ £ Z 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>i £ = i · 8 | s Q SJ_ φ Q_ O cl <sup>73</sup> AND</td>
<td>φφ'-Ε — δο ,. B £ g. δ -g φ " oo o-2 CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>o O ° zs Φ Φ 4; OR? Φ 2 1_ 2 (θ '2 -O CL φ 05 0- Ό -g E</td>
<td>¿2 ω i Φ Φ E Φ 2! _ B S 'g. or Q- .2 φ o “c ñJ o α. φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>Í £ ot φ | Í faith or Φ <sup>73</sup> Q_ O Q_ -o E</td>
<td>¿Φ g = 5 Φ Φ 4; E Φ 2 1_ B S 'g. 'or .2 ra α- φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<img file="ES2178232T5_D0042.tif" />
IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>i> = i 8 | í Q SJ_ φ Uí Q_ O CL <sup>73</sup> AND</td>
<td>2 £ § -gg% ω O í = CL o CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>i> = i? 8 I to Q s-l_ φ or Q_ O CL <sup>73</sup> AND</td>
<td>φφ ^ Ε— 2 ΈΓ g. or -gg% ω O í = CL o CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>c O ° zs <D <D ñp <D Φ L_ 2 oT g. -o cl or ra or- <sup>73</sup> -g E</td>
<td>2nd R Φ Φ l_ E Φ P 2 oT g. or Q- ra ° ~ “í = φ p α- <u -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>i> oi · í i S O Φ or O o_ ° E</td>
<td>¿<5 ° i φ Φ i- E Φ L> i_ 2 oT g. or Ω- Φ ° ~ <sup>c</sup> φ R or. o -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
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<img file="ES2178232T5_D0056.tif" />
<img file="ES2178232T5_D0057.tif" />
<img file="ES2178232T5_D0058.tif" />
<td>σ 'CO OI LO</td><td rowspan="2">σ 'Ο σ> Eoo 00</td><td rowspan="2">σ 'O CO or oo 00</td><td rowspan="2">σ 'Ο OI E- 00</td><td rowspan="2">σ 'O ECO CO ~ 00</td><td rowspan="2">σ 'O 00 3lo 00</td><td rowspan="2">σ IT IT 00</td><td rowspan="2">σ 'Ο ELO co 00</td><td rowspan="2">σ 'CO CO LO of 00</td><td rowspan="2">σ 'O σ> 00</td><td rowspan="2">σ '00 00 co o 00</td><td rowspan="2">σ 'LO CO OI σί E-</td><td rowspan="2">σO CO or oo E-</td><td rowspan="2">σ OI O 00 co E-</td><td>θ '* OI LO</td>
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<img file="ES2178232T5_D0062.tif" />
<img file="ES2178232T5_D0063.tif" />
<img file="ES2178232T5_D0064.tif" />
<img file="ES2178232T5_D0065.tif" />
<img file="ES2178232T5_D0066.tif" />
<img file="ES2178232T5_D0067.tif" />
<img file="ES2178232T5_D0068.tif" />
<img file="ES2178232T5_D0069.tif" />
<img file="ES2178232T5_D0070.tif" />
<img file="ES2178232T5_D0071.tif" />
<img file="ES2178232T5_D0072.tif" />
<img file="ES2178232T5_D0073.tif" />
<img file="ES2178232T5_D0074.tif" />
<td>σ ' 3CO CO</td><td>σ 'OI OI σ></td><td>σ ' 00 3-</td><td>σ ' 3- CO</td><td>σ 'EO</td><td>σ ' 3- CO</td><td>σ 00 00 co</td><td>σ 'CO OI E-</td><td>σ 'OI OI E-</td><td>σ ' 3- 00 CO</td><td>σ 'OO CO</td><td>σ 'CO O</td><td>σ33CO</td><td>σ 'CO IT</td><td>σ 'O OI σ></td>
<td>E- 00</td><td>co 00</td><td>co 00</td><td>what 00</td><td> 00</td><td>co 00</td><td>of 00</td><td> 00</td><td>or 00</td><td>σί E-</td><td>oo E-</td><td>E- E-</td><td>co E-</td><td>I E-</td><td>co E-</td>
<td>σ 'CO CO co</td><td rowspan="2">σ '00 E- Or co</td><td rowspan="2">σ 'OI LO 00 co</td><td rowspan="2">σ 'O LO CO</td><td rowspan="2">σ 'CO OR LO lo</td><td rowspan="2">σ 'CO 00 co co</td><td rowspan="2">σOI co AND-</td><td rowspan="2">σ 'EEOI oo</td><td rowspan="2">σ '00 EOI σί</td><td rowspan="2">σ 'CO CO or I HEARD</td><td rowspan="2">σ ' σ> co I HEARD</td><td rowspan="2">σ '3O LO Ol OI</td><td rowspan="2">σ 'CO LO CO co Ol</td><td rowspan="2">σ 'E- 3- 00 I HEARD</td><td>σ 'O 00 o</td>
<td>of</td><td>co Ol</td>
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<img file="ES2178232T5_D0076.tif" />
<img file="ES2178232T5_D0077.tif" />
<img file="ES2178232T5_D0078.tif" />
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<img file="ES2178232T5_D0082.tif" />
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<img file="ES2178232T5_D0085.tif" />
<img file="ES2178232T5_D0086.tif" />
<img file="ES2178232T5_D0087.tif" />
<img file="ES2178232T5_D0088.tif" />
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<td>σ 'CO Ol σ></td><td>σ 'Ol 00</td><td>σ ' OR</td><td>σ 'σ> or CO</td><td>σ 'EEE-</td><td>σ ' 3- σ></td><td>σ 3- OR</td><td>σ ' 3EO</td><td>σ 'Ol σ> o</td><td>σ 'σ> co o</td><td>σ ' 00 o o</td><td>σ 'σ> or σ></td><td>σ Ol EE-</td><td>σ 'σ> σ> LO</td><td>σ 'E00 CO</td>
<td>E- 00</td><td>E- 0 0</td><td>co 00</td><td>it 00</td><td> 00</td><td>co 00</td><td>co 00</td><td>of 00</td><td> 00</td><td>or 00</td><td>σί E-</td><td>E- E-</td><td>co E-</td><td>I E-</td><td>AND-</td>
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<td>of</td><td>what οι</td>
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<img file="ES2178232T5_D0092.tif" />
<img file="ES2178232T5_D0093.tif" />
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<img file="ES2178232T5_D0099.tif" />
<img file="ES2178232T5_D0100.tif" />
<img file="ES2178232T5_D0101.tif" />
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<img file="ES2178232T5_D0103.tif" />
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<img file="ES2178232T5_D0106.tif" />
<img file="ES2178232T5_D0107.tif" />
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E- LO Ol CO Ol co <r co eE- Y- Y- 'Rt
O 00 OI
<td> 3-</td><td>Ε-</td>
<td>Ε-</td><td>CD</td>
<td>οι</td><td> 00</td>
<td>ο</td><td>σ></td>
<td>ο</td><td> 00</td>
CO LO σ> co σ> co σ> or E- E-
<img file="ES2178232T5_D0109.tif" />
<img file="ES2178232T5_D0110.tif" />
<img file="ES2178232T5_D0111.tif" />
<img file="ES2178232T5_D0112.tif" />
IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>8 £ ° I · í 1 s O +> Φ or O o_ ° E</td>
<td>¿Φ "5 Φφ> -Ε-ζ: 2<sup>ο</sup>> - 2 ΈΓ g. or -g φ -g φ O ~ £ Z 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>2 g. f -g $ | ® Q φ Uí Q_ O cl φ E</td>
<td>φφ'-Ε— 2nd, _ 2 £ g. δ £ φ -g .2 o ~ c 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>or O ° z; Φ Φ 4; ¡Σ 'φ 2 L. 2 ¡σ 'g_ -O CL Φ ro 0- <sup>73</sup> -g E</td>
<td>¿2 ω i Φ Φ E Φ o 2 ¡σ 'g. o Q- .2 ro o “c ñJ o α. φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>? * s 1 «8 f S o - Φ o- O</td>
<td>¿G ω ό 2 ¡σ 'g. or -g φ α- φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<td>σ ' 33- CO</td><td rowspan="2">σ ' IT CO I heard CO</td><td rowspan="2">σ · OO CO l · - CO</td><td rowspan="2">σ 'hCM CM LO CO</td><td rowspan="2">σ 'LO OR co CO</td><td rowspan="2">σ 'O LO oo CO</td><td rowspan="2">σ '00 CO hoo LO</td><td rowspan="2">σ '00 CO LO co LO</td><td rowspan="2">σ 'CO LO co IT</td><td rowspan="2">σ '00 CO cm LO</td><td rowspan="2">σ CM O I heard</td><td rowspan="2">σ 'CO hl</td><td rowspan="2">σ 'CO CM LO LO</td><td rowspan="2">σ 'O) LO CO co</td><td rowspan="2">σ 'CO CM CM</td><td rowspan="2">σ '00 CM I heard co</td><td rowspan="2">σ 'LO h- O l - co</td><td rowspan="2">σO) CO or co</td><td>θ '* co</td>
<td>h-</td><td>co co</td>
<td>σ 'CO LO CO</td><td rowspan="2">σ 'O) 3CO or co</td><td rowspan="2">σ σ> CO cm co</td><td rowspan="2">σ 'CO hh- CO</td><td rowspan="2">σ 'LO O) 00 co co</td><td rowspan="2">σ 'O LO or I heard co</td><td rowspan="2">σ 'CM CO CM_</td><td rowspan="2">σ 'CM CO CO</td><td rowspan="2">σ '3- 3CO what</td><td rowspan="2">σ 'CM CO 00</td><td rowspan="2">σO) hO or LO</td><td rowspan="2">σ '300 CM cm LO</td><td rowspan="2">σ ' 3- h- IT</td><td rowspan="2">σ ' 3- CO co IT</td><td rowspan="2">σ 'hhhoo IT</td><td rowspan="2">σ 'CM h00 or CO</td><td rowspan="2">σ 'LO CM O) cm CO</td><td rowspan="2">σ ' CO OR) CO</td><td>σ 'h00 00</td>
<td>CO CM</td><td>co co</td>
N OJOJ
D OO
Ó ÓÓ
XXX
LO T-rco
CM CMCM
<img file="ES2178232T5_D0113.tif" />
<img file="ES2178232T5_D0114.tif" />
CNCN
OO
ÓÓ
XX τcoco cmcm cnCN oo
Óó
XX
CO00 coconut cmcm
CNCN oo
Óó
XX σ> or coco cmcm
<img file="ES2178232T5_D0115.tif" />
<img file="ES2178232T5_D0116.tif" />
CNCN
OO
ÓÓ
XX coσ>
colo cmcm
CNCN
OO
ÓÓ
XX ”3-σ>
lo ^ r cmcm
CNCN
OO
ÓÓ
XX
COh ”3-c or cmcm
<td>θ '* OR CM_</td><td>σ 'O 3- 00</td><td>σ · CM 33-</td><td>σ 'LO OO</td><td>σ ' 00 co IT</td><td>σ 'O) co o</td><td>σ ' IT</td><td>σ 'CO LO or</td><td>σ 'O) CO co</td><td>σ 'CO LO Γ ** -</td><td>σ LO</td><td>σ 'LO</td><td>σ 'LO LO Γ ** -</td><td>σ 'Γ ** - 3O</td><td>σ ' 3CM CO</td><td>σ 'OO) LO</td><td>σ ' 00 3- 00</td><td>σ 'CO OR</td><td>σ ' 00 LO co</td>
<td>r-</td><td>cm h-</td><td>h-</td><td>or h-</td><td>oo CO</td><td>CO</td><td>MAD</td><td>co CO</td><td>cm CO</td><td>or CO</td><td>HEARD IT</td><td>IT</td><td>LO LO</td><td>IT</td><td>cm LO</td><td>or LO</td><td>oo</td><td></td><td>it</td>
we are we are we are we are
O 'O' O 'O' O 'O' O 'O' O 'O' O 'O' O 'O' O 'O' O 'o'
<td>or</td><td>or</td><td> 00</td><td>IT</td><td>CM</td><td> 5—</td><td>ο</td><td>r-</td><td> 5—</td><td> 3-</td><td>IT</td><td>IT</td><td>IT</td><td>co</td><td>co</td><td>or</td><td>CM</td><td>Γ ** -</td><td>CM</td>
<td>or</td><td>co</td><td>IT</td><td>or</td><td>CO</td><td>CO</td><td> 00</td><td> 3-</td><td>co</td><td> 3-</td><td> 00</td><td>IT</td><td> 3-</td><td>IT</td><td>r-</td><td> 5—</td><td>IT</td><td>OR)</td><td> 3-</td>
<td>r-</td><td>X—</td><td>IT</td><td>or</td><td> 3-</td><td>ο</td><td></td><td>or</td><td>co</td><td>CM</td><td> 00</td><td>IT</td><td>CM_</td><td>OR)</td><td>co</td><td> 3-</td><td>x—</td><td> 00</td><td>CO</td>
<td>it</td><td></td><td>oo</td><td>I heard</td><td>V- ''</td><td>cm</td><td></td><td>co</td><td>l <</td><td>I heard</td><td>or</td><td>cm</td><td></td><td>it</td><td></td><td>I heard</td><td>5 — Γ</td><td>cm</td><td></td>
<td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>co</td><td>co</td><td>co</td><td>co</td><td>co</td><td>co</td><td></td><td></td><td></td><td></td><td></td><td></td><td>IT</td><td>IT</td><td>IT</td>
<img file="ES2178232T5_D0117.tif" />
<img file="ES2178232T5_D0118.tif" />
<img file="ES2178232T5_D0119.tif" />
<img file="ES2178232T5_D0120.tif" />
<img file="ES2178232T5_D0121.tif" />
<img file="ES2178232T5_D0122.tif" />
<img file="ES2178232T5_D0123.tif" />
<img file="ES2178232T5_D0124.tif" />
<img file="ES2178232T5_D0125.tif" />
<img file="ES2178232T5_D0126.tif" />
<img file="ES2178232T5_D0127.tif" />
<img file="ES2178232T5_D0128.tif" />
<img file="ES2178232T5_D0129.tif" />
<img file="ES2178232T5_D0130.tif" />
<img file="ES2178232T5_D0131.tif" />
<img file="ES2178232T5_D0132.tif" />
<img file="ES2178232T5_D0133.tif" />
<img file="ES2178232T5_D0134.tif" />
<img file="ES2178232T5_D0135.tif" />
we are we are we are we are
O 'O' O 'O' O 'O' O 'O' O 'O' O 'O' O 'O' O 'O' O 'O'
<td> 0</td><td>CM</td><td>OR)</td><td> 00</td><td>OR)</td><td>Γ ** -</td><td> 00</td><td>CO</td><td>OR)</td><td>co</td><td>IT</td><td> 00</td><td>co</td><td> 00</td><td>Γ ** -</td><td>IT</td><td> 5—</td><td> 5—</td><td> 0</td>
<td>IT</td><td> 3-</td><td>OR)</td><td> 5—</td><td>OR)</td><td> 3-</td><td>IT</td><td>co</td><td>Γ ** -</td><td>OR)</td><td>Γ ** -</td><td>CM</td><td>IT</td><td>IT</td><td> 3-</td><td>CM</td><td>OR)</td><td>IT</td><td> 5—</td>
<td>CO</td><td>co</td><td>OR)</td><td>CO</td><td>X—</td><td>h-</td><td>CM_</td><td>Γ ** -</td><td>X—</td><td>IT</td><td>OR)</td><td>co</td><td>CO</td><td>OR)</td><td>CM</td><td>IT</td><td>Γ ** -</td><td> 0</td><td>co</td>
<td>cm</td><td>ν '</td><td>I heard</td><td>co</td><td>l <</td><td>IT</td><td></td><td>cm</td><td>ν '</td><td>I heard</td><td>l <</td><td>co</td><td></td><td>cm</td><td>ν '</td><td>I heard</td><td></td><td>co</td><td></td>
<td>h-</td><td>h-</td><td>CO</td><td>CO</td><td>CO</td><td>CO</td><td>CO</td><td>CO</td><td>CO</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td>IT</td><td></td><td></td><td></td><td></td>
<td>σ 'or LO co</td><td rowspan="2">σ '00 LO CO 00 CM</td><td rowspan="2">σ or 0 0 co</td><td rowspan="2">σ 'CM 00 co co</td><td rowspan="2">σ ' o 00 cm co</td><td rowspan="2">σ 'co LO CM_ co</td><td rowspan="2">σ 'CM 3hLO co</td><td rowspan="2">σ '3CO CM l <CO</td><td rowspan="2">σ ' CM 00 00 CO</td><td rowspan="2">σ 'Γ ** O 3- OR</td><td rowspan="2">σ LO CM O cm</td><td rowspan="2">σ 'CM hCO co</td><td rowspan="2">σ 'h- 3CO what</td><td rowspan="2">σ 'CM 3O</td><td rowspan="2">σ 'CO LO h00</td><td rowspan="2">σ 'LO h- 3- OR WHAT</td><td rowspan="2">σ 'OO CM cm LO</td><td rowspan="2">σ 'O 3O co IT</td><td>σ 'OO CO</td>
<td>l <CM</td><td>what</td>
<td>ND</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN O</td><td>CN 0</td><td>CN O</td><td>CN O</td><td>CN O</td><td>CN O</td><td>CN 0</td><td>cn 0</td><td>CN 0</td><td>cn 0</td><td>cn 0</td><td>cn 0</td><td>cn 0</td><td>cn 0</td>
<td rowspan="4">or X 3LO</td><td rowspan="4">or X 0 LO</td><td rowspan="4">OR X co CO</td><td rowspan="4">or X hCO</td><td rowspan="4">OR X CM h-</td><td rowspan="4">OR X CO h-</td><td rowspan="4">OR X 0 00</td><td rowspan="4">OR X 3- 00</td><td rowspan="4">OR X 0 00</td><td rowspan="4">OR X CM O</td><td rowspan="4">OR X CO 0</td><td rowspan="4">OR X 0 0 cm</td><td rowspan="4">OR X co 0 cm</td><td rowspan="4">or X LO 0 cm</td><td rowspan="4">OR X h0 cm</td><td rowspan="4">OR X 0 0 cm</td><td rowspan="4">OR X 0 cm</td><td rowspan="4">OR X cm</td><td>OR</td>
<td>X</td>
<td></td>
<td>cm</td>
<td>σ 'CO co</td><td>σ 'LO 3- 00</td><td>σ LO IT</td><td>σ ' CO 3-</td><td>σ 'Ο CO h-</td><td>σ 'CO 0 CM</td><td>σ 'O CM 00</td><td>σ ' CO</td><td>σ 'O hh-</td><td>σ 'co 0</td><td>σ σ> LO</td><td>σ 'CO LO 0</td><td>σ ' 00 00 CM</td><td>σ ' 00 OR LO</td><td>σ 'O 00 00</td><td>σ 'CM CO</td><td>σ 'O</td><td>σ ' 3CO CO</td><td>σ 'co OO</td>
<td>co h-</td><td>h-</td><td>Or h-</td><td>HEAR CO</td><td>CO</td><td>co co</td><td>co</td><td>co co</td><td>co</td><td>0 co</td><td>00 LO</td><td>co LO</td><td>LO LO</td><td>co LO</td><td>IT</td><td>OR WHAT</td><td>OO</td><td>co</td><td></td>
<td>σ ' 3co 00</td><td rowspan="2">σ 'LO LO OO CM</td><td rowspan="2">σ LO 00 3rd CM</td><td rowspan="2">σ '3LO 00 0 co</td><td rowspan="2">σ ' CO CM cm CO</td><td rowspan="2">σ '3O hco co</td><td rowspan="2">σ 'O 00 mad</td><td rowspan="2">σ 'Ο 00 co co co</td><td rowspan="2">σ 'O co CM 00 CO</td><td rowspan="2">σ '3O 00 I heard co</td><td rowspan="2">σO) 0 3- 5</td><td rowspan="2">σ 'h- 3O co</td><td rowspan="2">σ ' CM h-</td><td rowspan="2">σ 'CM O 3co</td><td rowspan="2">σ ' oo</td><td rowspan="2">σ '00 CO 00 I heard</td><td rowspan="2">σ ' 00 IT IT</td><td rowspan="2">σ 'CO CO co co IT</td><td>σ ' 3O) 0</td>
<td>co CM</td><td>what</td>
<td>ND</td><td>CN O</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN 0</td><td>CN O</td><td></td><td rowspan="5">LO CM OO CM Or 0</td><td>CN O</td><td>cn 0</td><td>CN 0</td>
<td rowspan="4">or X CM LO</td><td rowspan="4">OR X CO LO</td><td rowspan="4">OR X co</td><td rowspan="4">OR X CO CO</td><td rowspan="4">or X 0 h-</td><td rowspan="4">OR X I h-</td><td rowspan="4">OR X O) h-</td><td rowspan="4">OR X co 00</td><td rowspan="4">or X h- 00</td><td rowspan="4">or X OR)</td><td rowspan="4">or X 3- OR)</td><td rowspan="4">or X 00 O)</td><td rowspan="4">or X CM Or cm</td><td rowspan="4">OR X LO 0 cm</td><td rowspan="3">h0 CM OO</td><td rowspan="4">OR X cm</td><td rowspan="4">OR X co cm</td><td>or</td>
<td>X</td>
<td>co</td>
<td></td><td>cm</td>
<td>h-</td><td>CO</td><td> 5—</td>
<td>IT</td><td>co</td><td>IT</td>
<td>h-</td><td>co</td><td>co</td>
<td> 5—</td><td>co</td><td>IT</td>
<td>CO</td><td>IT</td><td></td>
<td>h-</td><td>IT</td><td>IT</td><td>CO</td>
<td>h-</td><td> 0</td><td> 00</td><td>CM</td>
<td>h-</td><td>IT</td><td>h-</td><td>co</td>
<td>h-</td><td> 0</td><td>co</td><td>h-</td>
<td>co</td><td>co</td><td>CM</td><td>T—</td>
<img file="ES2178232T5_D0136.tif" />
<img file="ES2178232T5_D0137.tif" />
<img file="ES2178232T5_D0138.tif" />
<td>CM</td><td> 0</td>
<td>CM</td><td>co</td>
<td>h-</td><td> 0</td>
<td> 0</td><td>IT</td>
<td> 00</td><td> 00</td>
CM CO 00 CO LO CO O CO 00 hO CM h- 00 CO LO
CM 00 h- CO
<td>CM</td><td> 0</td>
<td> 0</td><td> 00</td>
<td> 0</td><td>IT</td>
<td> 3-</td><td> 5—</td>
<td>CO</td><td>CO</td>
IS 2 178 232 T5
<td rowspan="3">Comparative Example 4</td><td>i £ oto | i or Φ <sup>73</sup> Q_ O Q_ -o E</td>
<td>¿Φ Z5 φ φ s- E - 9 o. E «r g. or -g Φ £ ω o ~ c cl O CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>8> or I · í 1 s Q SJ_ φ Q_ O CL <sup>73</sup> AND</td>
<td>φφ-Ε- ° ο ^ E ΈΓ g. or -g φ ™ o ~ c 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>CO g =! φ φ a- ro 'φ 2 ιΒ ro' g. -a cl φ ro o-<sup>73</sup> -g E</td>
<td>¿Φ ω i Φ <D l. E Φ O ιΕ ra 'g. or -g Φ ° ~ <sup>c</sup> Φ g 0- Φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>Lh | S 8 IS Q s-l_ φ or Q_ O CL <sup>73</sup> AND</td>
<td>¿G ω i Is G. or rx φ ω o. Φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<img file="ES2178232T5_D0139.tif" />
SO SOsO
E- E-CM τ- 00ECO 00τ—
CO τ-o sO sOsO
CO LOEE- OCO
3- E- too COlo
CO COCO SO SOsO
O) O
O τ-CO
OCO co Άo
CO COCO SO SOsO
OR COCO
LO 00E00 COO oo E-lo
CM CMCM
<td>θ '* CO CO</td><td>σ 'OO CO</td><td>σO CO or</td>
<td>CM</td><td>co CM</td><td>cm CM</td>
SO SOsO
CO CO00 τ-CM
CO τ-00 co ooσ>
LOLO JUST JUST
E- Crazy
CM OCO
LO CM00 x- cotj
CO COCO sO sOsO τ- COO
O 00 * sT
O CO co ooσ>
co coco sO sO
OELO τ — CM τ- COO
Άcm
E- E-That sOsO
E- τ — O
00O
CO COO
THE COE-
E- EE-
<img file="ES2178232T5_D0140.tif" />
<img file="ES2178232T5_D0141.tif" />
<img file="ES2178232T5_D0142.tif" />
<img file="ES2178232T5_D0143.tif" />
<img file="ES2178232T5_D0144.tif" />
<img file="ES2178232T5_D0145.tif" />
<img file="ES2178232T5_D0146.tif" />
<img file="ES2178232T5_D0147.tif" />
<img file="ES2178232T5_D0148.tif" />
<img file="ES2178232T5_D0149.tif" />
<img file="ES2178232T5_D0150.tif" />
<img file="ES2178232T5_D0151.tif" />
<img file="ES2178232T5_D0152.tif" />
<img file="ES2178232T5_D0153.tif" />
<img file="ES2178232T5_D0154.tif" />
SO SOsO
00O
E- LOLO
LO 00τ— cm oσ>
co sO sOsO
LO τ-LO
LO 00CO
E- τ— E- lotJ co coco sO sOsO
CMCO
CMO
LO OtJ cm oσ>
CO COCM sO sOsO
X- CO O LO * sT σ> o
E- colo
CM CMCM SO SO
OO
CO C0τ—
C0 CM'r-
CM CMCM SO SO
CM CMO
CMLO x- 00
E- σ> o
THE CRAZY ONLY ONLY
LO OLO τ-CO
LO CM00
CMlo
CO COCO SO SOsO
COEE- LOO
OR WHAT
E- σ> o
CO COE SOsO
CO CDCM
OLO
O LOO
CM CO ”3 ·
E- E-That sOsO ce
CO CO τΟ OLO
C0 CO00
CO E-OO
E- EE-
<img file="ES2178232T5_D0155.tif" />
<img file="ES2178232T5_D0156.tif" />
<img file="ES2178232T5_D0157.tif" />
<img file="ES2178232T5_D0158.tif" />
<img file="ES2178232T5_D0159.tif" />
<img file="ES2178232T5_D0160.tif" />
<img file="ES2178232T5_D0161.tif" />
<img file="ES2178232T5_D0162.tif" />
<img file="ES2178232T5_D0163.tif" />
<img file="ES2178232T5_D0164.tif" />
<img file="ES2178232T5_D0165.tif" />
<img file="ES2178232T5_D0166.tif" />
<img file="ES2178232T5_D0167.tif" />
<img file="ES2178232T5_D0168.tif" />
<img file="ES2178232T5_D0169.tif" />
SO SOsO
Or CRAZY or
T- coco co To co sO sO
CO CMO
O 00EO τ-tJ
E- CO ”3 ·
C0 C0C0 SO SOsO
CO OtJ
O COE00 τ-LO
CMCD
C0 C0CM SO SOsO
OR LOC0
CM OC0
O LOO oo colo
CM CMCM sO sOsO cE τ-CO t- tJtJ
CO CMO) how
CM CMCM SO SO
T- LOTt
I smell it
COCO co ooo
THE CRAZY ONLY ONLY
Tj 00 το τ-CM
O 00LO cm colo
CO COCO SO SOsO
T- co O C0CM τ- 00TjE- OOO
CO COE SOsO
O LOE00 OCO
O you τ- COtJ
E- E-That sOsO
Or you
Lolo
CO EO co E-σ>
E- EE-
<img file="ES2178232T5_D0170.tif" />
<img file="ES2178232T5_D0171.tif" />
<img file="ES2178232T5_D0172.tif" />
<img file="ES2178232T5_D0173.tif" />
<img file="ES2178232T5_D0174.tif" />
<img file="ES2178232T5_D0175.tif" />
<img file="ES2178232T5_D0176.tif" />
<img file="ES2178232T5_D0177.tif" />
<img file="ES2178232T5_D0178.tif" />
<img file="ES2178232T5_D0179.tif" />
<img file="ES2178232T5_D0180.tif" />
<img file="ES2178232T5_D0181.tif" />
<img file="ES2178232T5_D0182.tif" />
<img file="ES2178232T5_D0183.tif" />
<img file="ES2178232T5_D0184.tif" />
<td> 3-</td><td> 00</td>
<td>CO</td><td>or</td>
<td>CO</td><td>co</td>
<td> 00</td><td>ITEM</td>
<td>ITEM</td><td>ITEM</td>
ECO CO CO OO Eco oo co CO CM
CM
<td>AND-</td><td> 5—</td>
<td>ITEM</td><td>CO</td>
<td>OR</td><td>or</td>
<td>OR</td><td>AND-</td>
<td></td><td>co</td>
CO lo E- O oo LO tJ co co
CO E-CO
CM CM το OLO
OO) ECO CMCM
IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>i £ oto | i faith or Φ <sup>73</sup> Q_ O Q_ -o E</td>
<td>¿Φ Z5 φ φ s- E - 9 o. 2 «r g. or -g φ " o ~ c oS CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>u ° hs 1 Q SL φ O Q_ o CL <sup>73</sup> AND</td>
<td>φφ-Ε- ° ο ^ Β oT g_ o -g φ " o ~ o o-2 CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>oo ° zs φ 05 l. ¡Σ 'Φ or 2 (θ '2 -O CL Φ 05 o ° Φ m ° 0- -a -g E</td>
<td>¿2 ω i Φ 05 l. E Φ o B oT g. o Ω- ro ° ~ ο φ 2 α. φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>i> = 1? sil Q s-l_ φ or Q_ O CL <sup>73</sup> AND</td>
<td>¿2 ω i φ φ E φ 2> _ B S 'g. o Ο- Φ ro o ~ “ο φ o α. φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<img file="ES2178232T5_D0185.tif" />
<td> 5—</td><td>or</td><td>co</td><td>CM</td><td> 00</td><td>co</td><td>or</td><td>co</td><td>OR</td><td> 3-</td><td> 3-</td><td>or</td><td> 5—</td><td>or</td><td>AND-</td><td> 00</td><td>or</td><td>co</td><td> 0</td>
<td></td><td> 00</td><td>AND-</td><td>CM</td><td>CM</td><td>or</td><td>CM</td><td>or</td><td> 3-</td><td> 3-</td><td>OR</td><td>or</td><td>co</td><td>AND-</td><td>IT</td><td>or</td><td> 5—</td><td> 0</td><td>IT</td>
<td>OR</td><td>T—</td><td>CM</td><td>CO</td><td>CO</td><td>CM</td><td>CM</td><td>T—</td><td>OR</td><td>AND-</td><td> 3-</td><td>τ-</td><td> 00</td><td> 3-</td><td>or</td><td>IT</td><td>T—</td><td>IT</td><td> 0</td>
<td>or</td><td>Y-''</td><td>cm</td><td>co</td><td></td><td>it</td><td>co</td><td>AND-</td><td>AND-</td><td>oo</td><td>σ></td><td>ο</td><td>or</td><td>Y-''</td><td>cm</td><td>cm</td><td>co</td><td>co</td><td></td>
<td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td> 0</td><td> 0</td><td> 0</td>
OCM
E- τ-CO
OR ECOCO
CM CMCM
<img file="ES2178232T5_D0186.tif" />
IS 2 178 232 T5
<td rowspan="3">Comparative Example 4</td><td>u ° hsi Q Φ Uí Q_ O CL <sup>73</sup> AND</td>
<td>φφ-Ε- ° ο ^ Β ΈΓ g. Ό -g φ% ω O ~ £ Z 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>i> = i · 8 | Ϊ Q Φ Uí Q_ O CL <sup>73</sup> AND</td>
<td>φφ'-Ε — δο ,. B £ g. or -g φ £ * oo o-2 CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>o O g zs Φ Φ s- ñp Φ o _ Β (θ 'S -a cl φ ra a- <sup>73</sup> -g E</td>
<td>¿2 ω i φ Φ Ε Φ or> _ B S 'g. or Q- .2 φ o ~ "C φ o Q- Φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>i £ ot φ | i (5 or Φ <sup>73</sup> q_ O Q_ -o E</td>
<td>¿<5 ω ό φ φ s- Ε φ 2 _ B ¡θ 'g. or Q- ro ° ~ <sup>c</sup> φ g a- φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<img file="ES2178232T5_D0187.tif" />
sO sOsO ”3- τΟ OO
O COTjoo oooo o oo sO sOsO
OElo o'sr
CO 00o oo oooo o oo sO sOsO
CO CMCO
E- O τΟ CMCO
O OO
O OO SO SOsO
THE 00O
T- OCO
Λ o oo o oo sO sOsO
OR E-LO
CM00
CO COEO OO
O OO
<img file="ES2178232T5_D0188.tif" />
<img file="ES2178232T5_D0189.tif" />
<img file="ES2178232T5_D0190.tif" />
<img file="ES2178232T5_D0191.tif" />
<img file="ES2178232T5_D0192.tif" />
<img file="ES2178232T5_D0193.tif" />
<img file="ES2178232T5_D0194.tif" />
<img file="ES2178232T5_D0195.tif" />
<img file="ES2178232T5_D0196.tif" />
<img file="ES2178232T5_D0197.tif" />
<img file="ES2178232T5_D0198.tif" />
<img file="ES2178232T5_D0199.tif" />
<img file="ES2178232T5_D0200.tif" />
<img file="ES2178232T5_D0201.tif" />
<img file="ES2178232T5_D0202.tif" />
SO SOsO
T- CMCO
E- COTT- E-CO co lolo sO sOsO
CO COECM COCM
OR LOCM ONLY SOsO
CO LOO
T- CMLO
O COCO COCO COCO SO SO
T- OTjO LOCM
OR 00CO
CO CMcm
<img file="ES2178232T5_D0203.tif" />
CM O CM cm cm sO sOsO σ> oo
CM CO00
00_ CM_CO co o oo sO sOsO
Tj E-CO
E- COEO Tj-Eio lolo
O OO SO SOsO
Tj LOO
E-LO
O COCO co coconut
O OO SO SOsO
OR OCO
OR LOEO T-CO
CO EE-
O OO SO SOsO
OO
CO COEIO EO
E- EE-
O OO
<img file="ES2178232T5_D0204.tif" />
<img file="ES2178232T5_D0205.tif" />
<img file="ES2178232T5_D0206.tif" />
<img file="ES2178232T5_D0207.tif" />
<img file="ES2178232T5_D0208.tif" />
<img file="ES2178232T5_D0209.tif" />
<img file="ES2178232T5_D0210.tif" />
<img file="ES2178232T5_D0211.tif" />
<img file="ES2178232T5_D0212.tif" />
<img file="ES2178232T5_D0213.tif" />
<img file="ES2178232T5_D0214.tif" />
<img file="ES2178232T5_D0215.tif" />
<img file="ES2178232T5_D0216.tif" />
<img file="ES2178232T5_D0217.tif" />
<img file="ES2178232T5_D0218.tif" />
SO SOsO
CM OR ECMCM
LO T-Eio lotj only sOsO
Tj oCO
O 00O tJ OEco sO sOsO
T- O) CM
T- CO00
I eat it just so
CMCO
CM CM E- LOCO cm cmcm SO SO
E- Tj-TCO COO
T- O00 cm t- ~ 'T-' · sO sOsO
OCO
E- 00LO tí COCM 'sr' srlo o oo sO sOsO
CO T-EO TO
THE OCM
The crazy
O OO SO SOsO
Or T-00
COTtJ EO
CO COE-
O OO SO SOsO
COELO E- ECMCO
E- EE-
O OO SO SOsO
CO COO
CO COO
OR TE- CO00
O OO
<img file="ES2178232T5_D0219.tif" />
<img file="ES2178232T5_D0220.tif" />
<img file="ES2178232T5_D0221.tif" />
<img file="ES2178232T5_D0222.tif" />
<img file="ES2178232T5_D0223.tif" />
<img file="ES2178232T5_D0224.tif" />
<img file="ES2178232T5_D0225.tif" />
<img file="ES2178232T5_D0226.tif" />
<img file="ES2178232T5_D0227.tif" />
<img file="ES2178232T5_D0228.tif" />
<img file="ES2178232T5_D0229.tif" />
<img file="ES2178232T5_D0230.tif" />
<img file="ES2178232T5_D0231.tif" />
<img file="ES2178232T5_D0232.tif" />
<img file="ES2178232T5_D0233.tif" />
<img file="ES2178232T5_D0234.tif" />
SO SOsO
CO CMEO CMO you COCM crazy
O OO SO SOsO
T- COO
CO 0000
LO 00 το coE-
O OO SO SOsO
COTLO T-LO
Tj EO
E- EE-
O OO SO SOsO
OR OCO
CO COLO
T- COLO co cooo o oo sO sOsO
CM 00CO
CM E-CM
E- COO oo ooo
O OO
COCONUT COCONUT
OO OO
Ó Ó ÓÓ
XX XX
CO LO oco
CM O OECM CM t- ~ t-
CO
LO or
<img file="ES2178232T5_D0235.tif" />
IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>i £ oto | i faith O Φ <sup>73</sup> or or Q_ E</td>
<td>¿Φ Z5 Φφ> -Ε-ζ: 2<sup>Ο</sup>ί_ E αΓ g. o -go -g ® o ~ c o. or CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>E # g. f -g I | ® Q SJ_ φ Q_ O CL <sup>73</sup> AND</td>
<td>φφ-Ε- ° ο ^ E ΈΓ g. or -g φ -g ® o ~ c 0-2 CL Φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>o O g = i Φ Φ L. (θ 'Φ o! _ E '¡σ' g - ° cl φ ro o- <sup>73</sup> -g E</td>
<td>¿Φ gi Φ <D L. E Φ O ΙΕ '¡σ' g. δ _g ra ° ~ <sup>c</sup> φ g or. φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>Lh S «8 1 S Q s-l_ φ or Q_ O CL <sup>73</sup> AND</td>
<td>¿Φ gi Φ Φ a- E Φ Φ> _ E '¡σ' g. or Ο- Φ ro o ~ “ο φ o or. φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<img file="ES2178232T5_D0236.tif" />
<img file="ES2178232T5_D0237.tif" />
<td>σ 'CO LO</td><td rowspan="2">σ ' OR CO co σ></td><td rowspan="2">σ ' 00 CO 3- co σ></td><td rowspan="2">σ '3O CO co σ></td><td rowspan="2">σ 'O CO E- CO σ></td><td rowspan="2">σ 'O 300 co σ></td><td rowspan="2">σ 'CO LO or co σ></td><td rowspan="2">σ 'LO LO OR σί o</td><td rowspan="2">σ E- 3- σί or</td><td rowspan="2">σ 'CO CO CM σί o</td><td rowspan="2">σ 'CM CM CO σί or</td><td rowspan="2">σ '3O 3σί or</td><td rowspan="2">σ '00 E- 3σί or</td><td rowspan="2">σ ' 3LO σί or</td><td rowspan="2">σ 'CM O LO σί o</td><td rowspan="2">σ ' 3- CO σί or</td><td rowspan="2">σ σ> co σί σ></td><td rowspan="2">σ 'CM 3Εσί σ></td><td>θ '* σ> 00 Ε-</td>
<td>co σ></td><td>σί σ></td>
<img file="ES2178232T5_D0238.tif" />
<img file="ES2178232T5_D0239.tif" />
<img file="ES2178232T5_D0240.tif" />
<img file="ES2178232T5_D0241.tif" />
<img file="ES2178232T5_D0242.tif" />
<img file="ES2178232T5_D0243.tif" />
<img file="ES2178232T5_D0244.tif" />
<img file="ES2178232T5_D0245.tif" />
<img file="ES2178232T5_D0246.tif" />
<img file="ES2178232T5_D0247.tif" />
<img file="ES2178232T5_D0248.tif" />
<img file="ES2178232T5_D0249.tif" />
<img file="ES2178232T5_D0250.tif" />
<img file="ES2178232T5_D0251.tif" />
<img file="ES2178232T5_D0252.tif" />
<img file="ES2178232T5_D0253.tif" />
<img file="ES2178232T5_D0254.tif" />
<img file="ES2178232T5_D0255.tif" />
<img file="ES2178232T5_D0256.tif" />
<img file="ES2178232T5_D0257.tif" />
<td>θ '* CM LO C0</td><td rowspan="2">θ '* 00 σ> 3- CO σ></td><td rowspan="2">θ '* LO C0 CO CO σ></td><td rowspan="2">θ '* CO Ε- CO σ></td><td rowspan="2">θ '* LO Ε- 00 CO σ></td><td rowspan="2">θ '* ΕΕσ> CO σ></td><td rowspan="2">θ '* 00 CO ο σί σ></td><td rowspan="2">θ '* σ> 3- σί σ></td><td rowspan="2">θ '* 3CM CM σί σ></td><td rowspan="2">θ '* 00 σ> CM σί σ></td><td rowspan="2">θ '* C0 Ε- C0 σί σ></td><td rowspan="2">θ '* LO 33σί σ></td><td rowspan="2">θ '* LO σί σ></td><td rowspan="2">θ '* Ο ΕΙΟ σί σ></td><td rowspan="2">θ '* ΕCM CO σί σ></td><td rowspan="2">θ '* CM 00 CO σί σ></td><td rowspan="2">θ '* C0 C0 Εσί σ></td><td rowspan="2">θ '* 3ΕΕσί σ></td><td>θ '* Ο 00</td>
<td>CO σ></td><td>σί σ></td>
<img file="ES2178232T5_D0258.tif" />
<img file="ES2178232T5_D0259.tif" />
<img file="ES2178232T5_D0260.tif" />
<img file="ES2178232T5_D0261.tif" />
<img file="ES2178232T5_D0262.tif" />
<img file="ES2178232T5_D0263.tif" />
<img file="ES2178232T5_D0264.tif" />
<img file="ES2178232T5_D0265.tif" />
<img file="ES2178232T5_D0266.tif" />
<img file="ES2178232T5_D0267.tif" />
<img file="ES2178232T5_D0268.tif" />
<img file="ES2178232T5_D0269.tif" />
<img file="ES2178232T5_D0270.tif" />
<img file="ES2178232T5_D0271.tif" />
<img file="ES2178232T5_D0272.tif" />
<img file="ES2178232T5_D0273.tif" />
<img file="ES2178232T5_D0274.tif" />
<img file="ES2178232T5_D0275.tif" />
<img file="ES2178232T5_D0276.tif" />
<td> 0,844%</td><td> 0,722%</td><td> 0,612%</td><td> 0,513%</td><td> 0,427%</td><td> 0,353%</td><td> 0,288%</td><td> 0,230%</td>
<td> 156%</td><td rowspan="2"> 99,278%</td><td rowspan="2"> 99,388%</td><td rowspan="2"> 99,487%</td><td rowspan="2"> 99,573%</td><td rowspan="2"> 99,647%</td><td rowspan="2"> 99,712%</td><td> 770%</td>
<td>σ> σ></td><td>Ο σ></td>
<td>θ '* Ο 00 θ '</td><td> 0,137%</td><td> 0,101%</td><td> 0,070%</td><td> 0,043%</td><td> 0,020%</td><td> 0,007%</td><td>θ '* Ο Ο Ο θ'</td>
<td> 820%</td><td rowspan="2"> 99,863%</td><td rowspan="2"> 99,899%</td><td rowspan="2"> 99,930%</td><td rowspan="2"> 99,957%</td><td rowspan="2"> 99,980%</td><td rowspan="2"> 99,993%</td><td>θ '* Ο Ο Ο</td>
<td>σ> σ></td><td>Ο ο</td>
<img file="ES2178232T5_D0277.tif" />
<img file="ES2178232T5_D0278.tif" />
<img file="ES2178232T5_D0279.tif" />
<img file="ES2178232T5_D0280.tif" />
<img file="ES2178232T5_D0281.tif" />
<img file="ES2178232T5_D0282.tif" />
<img file="ES2178232T5_D0283.tif" />
<img file="ES2178232T5_D0284.tif" />
<img file="ES2178232T5_D0285.tif" />
<img file="ES2178232T5_D0286.tif" />
<img file="ES2178232T5_D0287.tif" />
<img file="ES2178232T5_D0288.tif" />
<img file="ES2178232T5_D0289.tif" />
<img file="ES2178232T5_D0290.tif" />
<img file="ES2178232T5_D0291.tif" />
<img file="ES2178232T5_D0292.tif" />
CO co co
3rd co E36
IS 2 178 232 T5
Table 6 (Continuation)
<td rowspan="3">Comparative Example 4</td><td>2 g. f -g $ | ® Q φ Uí Q_ O CL <sup>7=5</sup> AND</td>
<td>φφ'-Ε— 9o, _ 2 £ g. δ £ ω ω O - £ Z 0-2 CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 3</td><td>i> = i sis Q φ Uí Q_ O CL <sup>73</sup> AND</td>
<td>φφ'-Ε — δο ,. 2 £ g. Ό -gg% φ oo o-2 CL φ E</td>
<td>Relative fraction</td>
<td rowspan="3">Example 2 of the invention</td><td>o O ° zs Φ Φ 4; ñp Φ 2 1_ 2 αΡ g_ -O CL φ 05 or “φ zr; ° 0- <sup>73</sup> -g E</td>
<td>¿Φ gi φ φ i- E φ 2 l. 2 ro * g. o Q. .2 ro o ~ "O φ o 0- φ -g E</td>
<td>Relative fraction</td>
<td rowspan="3">Comparative Example 1</td><td>Í £ ot φ | I faith or Φ<sup>73</sup> Q_O Q_ <sup>73</sup> AND</td>
<td>¿<5 ° i Φ φ> - E Φ ° X— 2 ro * g. o cl w o ~ ο φ ° o- φ -g E</td>
<td>Relative fraction</td>
<td></td><td>Molecular weight</td>
IS 2 178 232 T5
<td></td>
<td></td>
<td></td>
<td>sOsOsOsO Οτ-'ςΓοοΟΟ'ΤΟ COCOOCOCOt-OO tt-OOOOOO oooooooo</td>
<td>t-OCOE - ^^ coGD cocoococoooo2 οοοοοοοοοΗ. σί σί σί σί σί σί σί 2 00000002</td>
<td>sr ^ r ^ r ^ r ^ r ^ r ^ riOO φοοοοοοοο ΟΟΟΟΟΟΟΟο ΧΧΧΧΧΧΧΧχ EE-COCOt-O ^ EO 0 (0 ^ 0001 ^^ 100 LOt ^ -tTCOCOOIt- lo ο</td>
<td>SOsOsOsOsOsO ο ^ ce ce ce ce ce ce ce ce ce ce 000 ^^ - 0100 ^^ - 0 LOOIOE-LOCOt-t-OOO τ-τ-τ-ΟΟΟΟΟΟΟΟ ο ο ο ο ο ο ο ο ο ο ο</td>
<td>sOsOsOsOsO ^ 0 ^ 0 ^ 0 ^ 0 ^ 0 ^ 0 ^ 0 ^ 0 ^ 0 ^ 0 ^^ tt-ocoocot-ocoo2 ^ e-ooi ^ cocoooo2 OOOOOOOOOOOOoooooooooo2 00000000002</td>
<td>sr ^ r ^ r ^ r ^ r ^ r ^ r ^ riOiOtoS □ ooooooooooo OOOOOOOOOOOo XXXX XXXXXXXX OOILOO ^ t-OLOCOt-OIO E-CD ^ t-OOOILOt-t-OCOO CO CO CO CO OÍ OÍ 'b' τ- E- CO OO ~</td>
<td></td>
<td></td>
<td></td>
<td>010T-COCOCO ^ cO ^ o<sub>rr</sub>,<sub>rr</sub>, loe-Ot-t3 - [- ^ t-looco22 coLO '^' ^ rcooioiT-oogy</td>
IS 2 178 232 T5
From the unclean molecular weight data obtained by GPC in Table 6, Figures 21-22 were generated to provide high molecular weight / weight fraction comparisons between comparative compositions 1 and composition 2 of the invention and the composition comparative 3. These molecular weight comparisons indicate that Comparative Composition 3 includes a significant amount of ultra-high molecular weight material (i.e., approximately 0.2 weight percent of the composition has a molecular weight greater than or equal to 3.5 million grams / mole), while none of this ultra-high molecular weight material is present for Examples 1 and 2. Surprisingly, however, although Comparative Composition 3 contains a significant amount of ultra-high molecular weight material and exhibits good processability, this does not translate into improved tear resistance. That is, the compositions of the invention have tear strength equivalent to or greater than comparative composition 3 although the compositions of the invention do not contain such ultra-high molecular weight polymer parts. Thus, unexpectedly, the examples of the invention represent the ability to use higher compositional uniformity to compensate for lower molecular weight and still achieve excellent film tear strength and thus ultra-high molecular weights are not required to obtain excellent tear resistance of blown film.
In another evaluation, the effect on the product of I10 / I2 and the specific variations of the process were investigated at a nominal composition density of 0.918 g / cm<sup>3</sup>. In this evaluation, comparative composition 9 was compared to four other compositions, compositions 11-14. Compositions 11-14 were made using essentially the same polymerization system as described hereinbefore for Composition 2 of the invention. While the fresh comonomer (i.e. 1-octene) was fed only to the first reactor for the entire composition of the invention in the evaluation, Table 7 shows the specific variation in the weight percent fraction of the production of polymer between the first and second reactors as well as a variation in catalytic system injection and feed (ie ethylene and fresh comonomer). Figures 26 and 27 further illustrate the injection variation in this evaluation. Figure 26 shows the simultaneous injection of the Ziegler-Natta catalyst system and the feed of fresh make-up using a mechanical stirrer (i.e., a lightening mixer) and Figure 27 shows the separate injection of the Ziegler-Natta catalyst system and the feed of new supply as well as two injection points of the new supply feed.
A nominal 0.02mm blown film was made from the inventive compositions using a Sterling blown film unit equipped with an 8.9cm diameter 30: 1 L / D extruder and 20mm annular die. , 3 cm. The density, I2, I10 / I2 as well as the tear and impact behavior of the composition were measured and are also reported in Table 7.
Table 7 shows that compositions 12-14 exhibit a better balance of properties over comparative compositions 9 and 11. This product preference is attributed to a combination of product and process or system preferences as Table 7 indicates that compositions 12-14 are distinguished by (1) having an I10 / I2 in the range of 8 to 10.4 , (2) a fraction in the first reactor of less than 36 percent and (3) a separate injection of the catalyst system and the fresh feed as opposed to simultaneous introduction (such as, for example, as in Comparative Composition 9 where the catalyst and the fresh feed are injected together and mixed with the contents of the reaction stream in a mechanical mixer) or the catalyst system premix and the fresh feed.
Within the scope of the present invention, it appears that the most improved balance of properties is achieved when the fraction of the polymer in the first reactor is less than 36 percent by weight, preferably less than 31 percent by weight, more preferably less than or equal to 27 percent and when the fresh (neat) feed is injected into the reaction stream and some time is allowed to mix with the contents of the reaction stream before contacting the catalyst again contribution. In a continuous polymerization process, the delay between the injection of the fresh feed and the injection of the fresh catalyst is established by the design of the injector, the size of the polymerization system (lengths, diameters, etc. of the piping and equipment) and the speed of the reaction stream. Most preferably, in the present invention, the delay in injection time or contacting time is preferably at least 2 seconds and more preferably at least 5 seconds.
Separate injection or contacting and delayed mixing of the fresh catalyst and the fresh feed can be accomplished by any convenient means known in the art, including the use of a mechanical mixer for each injection point separately or a combination of a mechanical mixer at one injection point and a static mixer (eg a Kenix mixer) at the other injection point. However, preferably, static mixers are employed at the various injection points; that is, injection is achieved without the use of a mechanical mixer or stirring devices. Also preferably, the polymerization system is provided with at least two separate fresh feed injection points (multiple injection points) in at least one reactor.
IS 2 178 232 T5
Table 7
<img file="ES2178232T5_D0293.tif" />
<td>Impact per dart, grams</td><td>OR CN LO OR CN LO T- oo CN CN CN CO <sub>Λ</sub> CO E-</td>
<td>MD Elmendorf tear, g / mm</td><td>OO E- CN CO COCONLONO E- CO CN LO O CO E- O CO CN CN CN</td>
<td>Mixer at the injection point</td><td>q OOOO F - - - - “-4—> -4—> -4—> -4—> -ro -ra -ra -ra -ra O Ί- »Ί-» Ί- »Ί-» φ ω ω ω ω LU LU LU LU</td>
<td>New contribution of comonomer to reactor No.</td><td> - - - - -</td>
<td>Polymer fraction *</td><td>CO LO E- CO LO ~ CO θ 'or ~ lo' CN CO CO CN</td>
<td>CN OR</td><td>CN CO <sub>m</sub> C- 00 cocogx-x- Or or <sub>ra</sub>- oo</td>
<td>c _ E - or OR)</td><td> ,<sub>n</sub> 00 T- E- LO Ν 'LO Ν' Oooo</td>
<td>Composition density</td><td>00 CN m CN CD 00 00 ~ 00 E- σ> σ> σ> σ> θ 'θ' ° θ 'θ'</td>
<td>Example</td><td>Comparative Example 9 Comparative Example 11 Example 12 of the invention Example 13 of the invention Example 14 of the invention</td>
<img file="ES2178232T5_D0294.tif" />
IS 2 178 232 T5
In another evaluation, the effect on the product of I10 / I2 and the specific variations of the process were investigated at a nominal composition density of 0.927 g / cm<sup>3</sup>. In this evaluation, compositions 1 and 2 were compared with composition 15 of the invention. Comparative Composition 15 was manufactured using essentially the same polymerization system as described hereinbefore for Composition 2 of the invention. 5 Kenix static mixers were used at the various injection points as shown in Figure 27 for all of the three compositions of the invention. Table 8 shows that the polymer fraction was essentially the same for all three compositions of the invention, however, composition 1 of the invention differed from the other two by having the fresh comonomer injected into the second reactor as opposite. to the first reactor.
A nominal 0.08mm blown film was made from these inventive compositions using a Macro blown film unit equipped with a 6-inch annular die at a die pitch of 1mm. Density, I<sub>2</sub>, I<sub>10</sub>/ I<sub>2</sub> as well as the tear and impact behavior of the various compositions and are also reported in Table 8.
IS 2 178 232 T5
Table 8
<img file="ES2178232T5_D0295.tif" />
<td>Impact per dart, grams</td><td>co e- <r T- IO or ω ω</td>
<td>MD Elmendorf tear, g / mm</td><td>co what 00 S 00 g CO O °</td>
<td>Mixer at the injection point</td><td>static static static</td>
<td>New contribution of comonomer to reactor No.</td><td>Ol v- v-</td>
<td>Polymer fraction *</td><td>co co ooo co co co</td>
<td>CM OR</td><td>CO LO E- I heard co oo</td>
<td>c _ E - or</td><td>co or LO ”3- co <sup>or</sup>< oo °</td>
<td>Composition density</td><td> 0,927 0,9274 0,9275</td>
<td>Example</td><td>Comparative example 1 Example 2 of the invention Comparative example 15</td>
<img file="ES2178232T5_D0296.tif" />
IS 2 178 232 T5
With respect to comparative compositions 1 and 15, Table 8 shows that composition 2 of the invention exhibits a better balance of properties, and thus composition 2 of the invention represents an especially preferred embodiment of the present invention. The improved balance of properties incorporated by composition 2 of the invention is also attributed to a combination of product and process or system preferences. That is, Table 8 indicates that composition 2 of the invention is distinguished by (1) having an I10 / I2 in the range of 8 to 10.4, (2) separate injection of the catalytic system and the fresh feed and (3) feed of fresh (neat) comonomer into the first reactor (as opposed to I10 / I2 ratios greater than 10.4 for both comparative compositions 1 and 15 and the injection of fresh comonomer in the second reactor with regard to the comparative composition 1). Therefore, in especially preferred embodiments, the fresh comonomer is initially injected separately into the polymerization system, for example, but not limited to, in the first reactor of a multiple reactor system, where the first reactor refers to the reactor furthest from the product outlet.
In another evaluation, the effect of the melt index and the percentage conversion of ethylene in the process were investigated at a nominal composition density of 0.916 g / cm<sup>3</sup> - 0.918 g / cm<sup>3</sup>. In this evaluation, compositions 16-19 were manufactured using essentially the same polymerization system as described hereinbefore for composition 12. In particular, static mixers were employed and the new comonomer feed was directed to the first reactor of the two-reactor polymerization system and injected separately from the catalyst feed, the comonomer flow was adjusted to provide the compositional density per sample. Listed in Table 9, the hydrogen flow was controlled in each reactor to provide the melt index and I values.<sub>10</sub>/ I<sub>2</sub> Listed by sample in Table 9 and the fraction of the polymer in the first reactor was as indicated by sample in Table 9. The percent ethylene conversion in the first reactor was varied by known techniques (for example by controlling the rate catalyst feed to reaction stream).
A nominal 0.08mm blown film was made from these inventive compositions using a Macro blown film unit equipped with a 6 inch annular die with a die gap of 1mm. The density, I2, I10 / I2 as well as the tear and impact behavior of the various compositions were measured. Impact per dart was determined using a modification of ASTM D-1709 Method A (i.e. a 3 kg weight was used) since the film samples did not break under the standard test (i.e. the values were all greater than 850 grams). In addition to the procedure and product details, the Table also provides the tear and impact performance properties of Composition 16-19 as compared to Composition 12.
IS 2 178 232 T5
Table 9
<td>Impact per dart, grams</td><td>CM CO Ε- X ”3- T- CM CD E- 00 CD 00</td>
<td>MD Elmendorf tear, g / mm</td><td>Ett-CM ^ E- CO O CD CD CO CO E- CD O E- ”3- 00 E- σ></td>
<td>Tdpt above 75 ° C</td><td>oo oo cd O ~ O ~ O ~ θ 00 00 00 00 00</td>
<td>00 00 or T5 T5 Φ</td><td>T- ”3- CO CD CM co cm oo lo o CO CO CM CO CO</td>
<td>00 ο <:</td><td>OR I CO o V- lo V- cd CO CO CM CO CM</td>
<td>CS Ε S</td><td>° _ CM_ m</td>
<td>Conversion of C2 in percent</td><td>LO co co oo Ε- Ε- E- 00 00</td>
<td>* Polymer * fraction</td><td>IO E- CO CO E- or what CO CM CM CM CM</td>
<td>CM OR</td><td>00 CD CO OR CO CO CO O t— CO oo oo oo oo oo</td>
<td>c _ E CM - or CD</td><td>co co or cm i- ooooo</td>
<td>Composition density</td><td>OR CO CO LO OOOOLOOOE- cd cd cd cd cd ooooo</td>
<td>Example</td><td>Example 12 of the invention Comparative Example 16 Example 17 of the invention Example 18 of the invention Example 19 of the invention</td>
<img file="ES2178232T5_D0297.tif" />
O Ό
C
Φ ω
φ c 'E φ
+-»
Φ σ φ
ω
σ) φ ω
Ο ο ΙΟ ΕΦ
Ό
Φ
Ε ο
C φ ο ο_
IS 2 178 232 T5
The results in Table 9 show that composition 19 of the invention exhibits an outstanding balance of properties, as it surprisingly had the highest tear strength and impact strength of all the samples evaluated even though its melt index was relatively high. Therefore, composition 19 of the invention represents the most preferred embodiment of the present invention in which, in addition to being characterized by having an I10 / I2 in the range of 8 to 10.4 and that it is manufactured using the separate injection of the catalytic system and the fresh feed and by injecting the fresh feed (pure) comonomer into the first reactor, This most preferred embodiment of the present invention is further characterized by having an I10 / I2 in the range of 8 to 8.5, being manufactured using a fraction of the polymer in the first reactor that is relatively low (that is, less than or equal to 27 weight percent) and by controlling the weight percent of the comonomer conversion for the first reactor at a relatively high level (i.e. greater than 75 weight percent, more preferably greater than or equal to 80 weight percent and most preferably greater than or equal to 87 weight percent).
Contents153
328 sheets
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29 members in 18 offices
Priority claims14
| Document | Office | Kind | Date |
|---|---|---|---|
| 53263P | United States of America | – | |
| 5326397 | United States of America | P | |
| 5326397 | United States of America | P | |
| 63390P | United States of America | – | |
| 6339097 | United States of America | P | |
| 6339097 | United States of America | P | |
| 9813854 | United States of America | W | |
| 9813854 | United States of America | W | |
| 53263P | – | – | – |
| 63390P | – | – | – |
| PCTUS199813854 | – | – | – |
| US19970053263P | – | – | – |
| US19970063390P | – | – | – |
| WO1998US13854 | – | – | – |
Members29
| Document | Office | Kind | |
|---|---|---|---|
| CA2296635A1 | Canada | A1 | |
| WO9903902A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU8286298A | Australia | A | |
| NO20000279D0 | Norway | D0 | |
| ZA986434B | South Africa | B | |
| NO20000279L | Norway | L | |
| EP0996651A1 | European Patent Office (EPO) | A1 | |
| TR200000180T2 | Türkiye | T2 | |
| CN1265119A | China | A | |
| PL338511A1 | Poland | A1 | |
| HU0003291A2 | Hungary | A2 | |
| HUP0003291A2 | Hungary | A2 | |
| KR20010022071A | Republic of Korea | A | |
| AR016770A1 | Argentina | A1 | |
| JP2001512147A | Japan | A | |
| BR9810771A | Brazil | A | |
| US6319989B1 | United States of America | B1 | |
| AU744972B2 | Australia | B2 | |
| EP0996651B1 | European Patent Office (EPO) | B1 | |
| AT223445T | Austria | T | |
| ATE223445T1 | Austria | T1 | |
| US6451916B1 | United States of America | B1 | |
| DE69807702D1 | Germany | D1 | |
| ES2178232T3 | Spain | T3 | |
| DE69807702T2 | Germany | T2 | |
| CA2296635C | Canada | C | |
| EP0996651B2 | European Patent Office (EPO) | B2 | |
| ES2178232T5This record | Spain | T5 | |
| DE69807702T3 | Germany | T3 |
Numbers
- Publication
- 2178232
- Publication, DOCDB
- 2178232
- Publication, EPODOC
- ES2178232T
- Application
- 98933129
- Application, DOCDB
- 98933129
- Application, EPODOC
- ES19980933129T
Titles2
- Spanish
- COMPOSICIONES INTERPOLIMERAS DE ETILENO DE AMPLIA DISTRIBUCION DE PESOS MOLECULARES Y COMPOSICION UNIFORME, PROCEDIMIENTO PARA SU FABRICACION Y ARTICULOS PRODUCIDOS CON ELLAS.
- English
- INTERPOLIMERAL ETHYLENE COMPOSITIONS OF LARGE DISTRIBUTION OF MOLECULAR WEIGHTS AND UNIFORM COMPOSITION, PROCEDURE FOR MANUFACTURING AND ARTICLES PRODUCED WITH THEM.
Classification
- CPC, 10
- C08F210/16
- C08J5/18
- B01J8/0015
- B01J19/2435
- C08F10/02
- C08F110/02
- C08J2323/08
- C08L23/04
- C08L2205/02
- C08L23/0815
- IPC, 14
- C08F210 02
- C08L23 04
- C08J5 18
- B01J19 24
- B01J8 00
- B29C55 28
- B29K23 00
- B29L7 00
- B29L9 00
- B32B27 32
- C08F2 01
- C08F10 02
- C08F110 02
- C08F210 16