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 contribution of 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 10 2 melting point ratio, from 8 to 10.4, an Mw / Mn ratio greater than 4 as determined by gel chromatography, an I2 melt index 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 in the temperature of the dominant peak greater than 75 0 C, as determined by fractionation of crystallographic analysis in the range of from 20 to 100 0 C, equal to or greater than the mathematical product of 1.7946x10 -28 x 10 31.839 x composition density, a composition density in grams / cubic centimeters. The new composition exhibits good processability and improved toughness properties, especially excellent film resistance to breakage and impact, and is particularly applied for use in applications such as long-lasting coating of the interior of garbage cans and making very resistant bags.

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19 claims: 3 independent, 16 dependent
- 1ES 2 178 232 T3 REIVINDICACIONES 1. Un procedimiento y sistema de polimerizacioón de etileno para preparar una composicioón de polólmero de etileno, comprendiendo el sistema al menos dos puntos de inyeccioón y al menos dos reactores de polimerizacioón, teniendo cada reactor una corriente o zona de reaccioón en la que al menos se inyecta un sistema catalóltico y la alimentacioón de nuevo aporte y en el que la alimentacioón de nuevo aporte comprende etileno y opcionalmente al menos un comonóomero insaturado, comprendiendo el procedimiento operar en continuo los al menos dos reactores de polimerizacióon e inyectar separadamente el sistema catalóltico y la alimentacióon de nuevo aporte en la corriente o zona de reaccioón de al menos un reactor, comprendiendo la composicióon etileno interpolimerizado con al menos un comonóomero insaturado y caracterizada por tener:a) una relacioón de fluidez, I10/I2, desde 8 a 10,4, b) una Mw/Mn de superior a 4 seguón se determina mediante cromatografóla de permeabilizacióon a travóes de gel, c) un ólndice de fluidez, I2, desde 0,1 a 10 gramos/10 minutos, d) una densidad de la composicióon inferior a 0,945 gramos/centólmetro cuóbico, y e) basado en el peso total de partes de polólmero cristalizable, un porcentaje en peso a la temperatura móxima dominante por encima de 75°C, segun se determina usando la tecnica del fraccionamiento para el anólisis de la cristalizacion en el intervalo de 20 a 100°C, igual a o superior al producto matemóatico de 1,7946 x 10 -28 x 10 (31,839 x densidad de la composicioón) con la densidad de la composicioón expresada en gramos/centólmetro cuóbico.
- 2Una composicióon de polólmero que comprende etileno interpolimerizado con al menos un comonóomero insaturado, en la que la composicioón se caracteriza por tener:a) una relacioón de fluidez, I10/I2, desde 8 a 10,4, b) una Mw/Mn de superior a 4 seguón se determina mediante cromatografóla de permeabilizacióon a travóes de gel, c) un ólndice de fluidez, I2, desde 0,1 a 10 gramos/10 minutos, d) una densidad de la composicioón inferior a 0,945 gramos/centólmetro cuóbico, y e) basado en el peso total de partes de polólmero cristalizable, un porcentaje en peso a la temperatura móxima dominante por encima de 75° C, segun se determina usando la tecnica del fraccionamiento para el analisis de la cristalización en el intervalo de 20 a 100°C, igual a o superior al producto matemóatico de 1,7946 x 10 -28 x 10 (31,839 x densidad de la composicióon) con la densidad de la composicioón expresada en gramos/centólmetro cuóbico.
- 3Un artólculo fabricado que comprende la composicióon de interpolólmero de etileno definida en la reivindicacióon 2.
- 4El artólculo fabricado de acuerdo con la reivindicacióon 3, en el que el artólculo es una pelólcula, capa de pelólcula, revestimiento, pieza moldeada, bolsa, saco, parche o laómina.
- 5El artólculo fabricado de acuerdo con la reivindicacioón 4, en el que la pelólcula es una pelólcula monocapa.
- 6El artólculo fabricado de acuerdo con la reivindicacioón 4, en el que la pelólcula es una pelólcula multicapa.
- 7El artólculo fabricado de acuerdo con la reivindicacioón 4, en el que la pelólcula es una pelólcula soplada.
- 8La composicioón de acuerdo con la reivindicacioón 1, en la que el al menos un comonoómero 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. ES 2 178 232 T3
- 9La composicióon de acuerdo con la reivindicacioón 1, en la que el al menos un comonóomero insaturado es una α-olefina C 3 -C 20 .
- 10La composicióon de acuerdo con la reivindicacioón 1, en la que el interpolómero es un copolómero de etileno y 1-octeno.
- 11El procedimiento y el sistema de acuerdo con la reivindicacioón 1, en el que uno de los al menos dos reactores es un reactor de circuito cerrado de recirculacióon.
- 12El procedimiento y el sistema de acuerdo con la reivindicacióon 1, en el que los al menos dos reactores son reactores de circuito cerrado de recirculacioón.
- 13El procedimiento y el sistema de acuerdo con la reivindicacioón 1, en el que el procedimiento no se opera adiabóaticamente.
- 14El procedimiento y el sistema de acuerdo con la reivindicacióon 13, en el que el sistema comprende ademaós al menos un aparato de cambio de calor que separa el calor de reaccióon o de polimerizacioón de la corriente de reaccion del procedimiento a una intensidad de al menos 7,4 kw/m 3 -°K.
- 15El procedimiento y el sistema de acuerdo con la reivindicacioón 1, en el que la inyeccióon separada proporciona un retraso en la puesta en contacto y mezcla entre el catalizador inyectado y la alimentacioón de nuevo aporte inyectada de al menos 2 segundos.
- 16El procedimiento y el sistema de acuerdo con la reivindicacióon 1, en el que se emplean mezcladores estóaticos en los puntos de inyeccióon de la alimentacioón de nuevo aporte.
- 17El procedimiento y el sistema de acuerdo con la reivindicacioón 1, en el que se emplean mezcladores estóaticos en los puntos de inyeccióon del catalizador y de la alimentacióon de nuevo aporte.
- 18El procedimiento y el sistema de acuerdo con la reivindicacióon 1, en el que el sistema comprende ademaós al menos dos puntos de inyeccióon de alimentacioón de nuevo aporte.
- 19El procedimiento y el sistema de acuerdo con la reivindicacióon 1, en el que el comonoómero de nuevo aporte se inyecta en el primer reactor. NOTA INFORMATIVA:Conforme a la reserva del art. 167.2 del Convenio de Patentes Europeas (CPE) y a la Disposición Transitoria del RD 2424/1986, de 10 de octubre, relativo a la aplicación del Convenio de Patente Europea, las patentes europeas que designen a España y solicitadas antes del 7-10-1992, no producirán ningún efecto en España en la medida en que confieran proteccion a productos químicos y farmacáuticos como tales. Esta informacioán no prejuzga que la patente estáeonoincluáda en la mencionada reserva.
Independent claims19
272 paragraphs in 33 sections, as filed
IS 2 178 232 T3
DESCRIPTION
Ethylene interpolymeric 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 wide molecular weight distribution (MWD) and improved composition 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 of the film, and is particularly well suited for use in applications such as high performance garbage bin liners and plastic bags. transportation of heavy loads.
In the manufacture of ethylene interpolymers such as ethylene interpolymerized with at least one unsaturated comonoomer, a number of polymerization methods and processes 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 catalytic systems are described to provide uniform compositional and narrow MWD products (eg, EXACT plastoimers commercially supplied by Exxon Chemical Corporation) when used in a high pressure polymerization system and inversely products with decreased homogeneity with respect to short chain branching distribution and wider molecular weight distribution (for example, 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 manufacturing capabilities still does not allow the manufacture of ethylene interpolymer compositions characterized by having good processability and excellent toughness properties such as excellent impact resistance. and the tearing of the film. That is, known ethylene interpolymer compositions (either as single reactor products, multiple 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 the manufacture of blown film with sufficient melt strength to allow, for example, good stability to bubble formation to maximize productivity) and excellent toughness.
Traditional polyethylene dissolution to achieve improved toughness properties involves making 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 a basic linear polymer structure, the uniformity of the composition has been offered to achieve improved toughness properties. However, while the combination of a narrow molecular weight distribution, a basic linear polymer structure, and uniformity of composition 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 a narrow molecular weight distribution, increased compositional uniformity, and a basic linear polymer structure, to achieve the balance of good workability (i.e. resistance to melt fracture and bulk strength). cast) and toughness properties, Lai et al. describe in US Pat. Number 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 No. 5,210,142 and by Hazlitt et al. In US Patent No. 5,370. 940. However, while such polymer blends exhibit good workability and workability properties, known polymer blends inevitably exhibit insufficient compositional uniformity.
ES 2 178 232 T3 to provide the desired toughness properties.
Since no known ethylene interpolymer composition provides the desired balance of good to excellent processibility, resistance to melt fracture, 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 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 materials can be manufactured economically. molecular weights and / or densities of the product. There is also a need for a blown film with good extrudability and high resistance to impact and tear. 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 also still possesses a relatively high composition uniformity with respect to its short chain branching distribution or its fractional crystallinity. One aspect of the invention is an ethylene polymerization process and system for preparing an ethylene polymer composition, the system comprising at least two injection points and at least two polymerization reactors, each reactor having a stream or reaction zone in which at least one catalytic system is injected and the fresh feed is injected and in which the fresh feed comprises ethylene and optionally at least one unsaturated comonoimer, the process comprising the continuous operation of at least two polymerization reactors and the separate injecting of the catalytic system and the feed of new supply into the reaction stream or zone of at least one reactor, the composition comprising ethylene interpolymerized with at least one unsaturated comonomer and characterized by having:
a) a fluidity ratio, I10 / I2, from 8 to 10.4,
b) a Mw / Mn greater than 4 seconds is determined by permeabilization chromatography through gel,
c) a melt index, I2, from 0.1 to 10 grams / 10 minutes,
d) a composition density less than 0.945 grams / cubic centimeter, and
e) based on the total weight of parts of crystallizable polymer, a weight percentage at the maximum dominant 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 product <sub>1.7946 x 10 math</sub><sup>-28</sup> x 10<sup>(31.839x density of composition)</sup> with the density of the composition expressed in grams / cubic centimeter.
A third aspect of the invention is a polymer composition comprising ethylene interpolymerized with at least one unsaturated comonomer, wherein the composition is characterized by having:
a) a fluidity ratio, I10 / I2, from 8 to 10.4,
b) a Mw / Mn greater than 4 seconds is determined by permeabilization chromatography through gel,
c) a melt index, I2, from 0.1 to 10 grams / 10 minutes,
d) a composition density less than 0.945 grams / cubic centimeter, and
e) based on the total weight of crystallizable polymer parts, a weight percentage at the maximum dominant temperature above 75<sup>°</sup>C, is then determined using the fractionation technique for analysis of crystallization in the range of 20 to 100<sup>°</sup>C, equal to or greater than the product <sub>1.7946 x 10 mathematician</sub><sup>-28</sup> x 10<sup>(31.839x density of composition)</sup> with the density of the composition expressed in grams / cubic centimeter.
The fourth aspect of the invention is a manufactured article comprising an ethylene interpolymer composition, the composition comprising ethylene interpolymerized with at least one unsaturated comonoimer and characterized by having:
IS 2 178 232 T3
a) a fluidity relationship, I<sub>10</sub>/ I<sub>2</sub>, from 8 to 10.4,
b) an M<sub>w</sub>/ M<sub>n</sub> greater than 4 as determined by gel permeation chromatography,
c) a flow onyx, I2, greater than 0.1 grams / 10 minutes,
d) a composition density less than 0.945 grams / cubic centimeter, and
e) based on the total weight of parts of crystallizable polymer, a weight percentage at the maximum dominant 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 product <sub>1.7946 x 10 math</sub><sup>-28</sup> x10<sup>(31.839 x composition density)</sup> with the density of the composition expressed in grams / cubic centometer.
Overall, the invention represents the ability to separate I10 / I2, MWD, and uniformity of composition into substantially independent properties and achieve a previously unknown combination of these intronsic properties as well as a previously unknown combination of behavioral properties.
Figure 1 is a graph of the weight percent crystallized at the dominant maximum temperature above 75<sup>°</sup>C, determined using a fractionation technique for crystallization analysis (i.e., equipment for fractional separation CRYSTAF<sup>TM</sup>, computer program and procedures as provided by PolymerChar) in the range of 20 to 100<sup>°</sup>C and based on the total amount of parts of crystallizable polymer, for the compositions of the invention and the comparative compositions as a function of the density of the composition.
Figure 2 is a CRYSTAF curve for composition 1 of the invention that includes 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 that includes 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 that includes 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 that includes the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 6 is a CRYSTAF curve for comparative composition 5 that includes the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 7 is a CRYSTAF curve for comparative composition 6 that includes the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 8 is the CRYSTAF curve for composition 7 of the invention that includes 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 that includes the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
Figure 10 is a CRYSTAF curve for composition 9 of the invention that includes the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the respective maximum temperatures.
IS 2 178 232 T3
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 that compares the distribution of the short chain branching as it relates to the average molecular weight determined by viscometry (Mv) of composition 1 of the invention and comparative composition 3.
Figure 14 is an ATREF-DV curve that compares the distribution of the short chain branching as it relates to the average molecular weight determined by viscometry (Mv) of composition 2 of the invention and comparative composition 3.
Figure 15 is an ATREF-DV curve comparing the distribution of the short chain branching as it relates to the average molecular weight determined by viscometry (Mv) of compositions 1 and 2 of the invention.
Figure 16 is an ATREF-DV curve that compares the distribution of the short chain branching as it relates to the average molecular weight determined by viscometry (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 permeabilization chromatography (GPC) curves of compositions 1 and 2 of the invention.
Figure 20 is a comparison of the gel permeabilization 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 against 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 the 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 the comparative composition
3.
Figure 24 is a graph of blown film tear strength as a function of weight percent of the crystallized polymer portion at the dominant maximum temperature above 75 ° C for compositions 1 and 2 of the invention and compositions comparative 3 and 4.
Figure 25 is the CRYSTAF curve for composition 11 of the invention that includes the maximum temperature assignments and the integration of the weight fraction for the areas corresponding to the 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 the separate injection and mixing of the catalyst and the feed. again add using static mixers.
IS 2 178 232 T3
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 maximum dominant temperature above 75 ° C as a function of the density of the composition. The percentage by weight crystallized at the maximum dominant temperature was determined by the fractionation technique for the analysis of crystallization in the range of 20 to 100 ° C. Compared to comparative compositions, Figure 1 indicates that a composition of the present invention has higher amounts of higher crystallization polymer parts at equivalent compositional densities. Such increases in the higher crystallization polymer portions produce 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 composition 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 shows 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 essentially reflected a pronounced polymer part with a plateau occurring at a maximum temperature lower than that corresponding to the pronounced polymer part. .
Conversely, the CRYSTAF curve of a conventional heterogeneously branched ethylene polymer (Figure 6), such as DOWLEX LLDPE (linear low-density polyethylene) resin<sup>TM</sup> 2045, an ethylene / 1-octene copolymer of density 0.920 g / cm<sup>3</sup> and I2 melt onyx of 1.0 supplied by The Dow Chemical Company, 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 converted into a film form. In particular, it was surprisingly discovered that a composition having a broad molecular weight distribution to achieve good processability can be manufactured with optimized composition uniformity and thus ensure that manufactured articles prepared therefrom will exhibit a improved toughness.
The expression "maximum dominant temperature" as used here refers to the maximum temperature as determined from the fractionation technique for the analysis of crystallization in the range of 20 to 100 ° C which represents and corresponds to the percentage by weight which Highest crystallizable polymer part 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 a maximum temperature that represents and corresponds to the highest percentage by weight of parts of
ES 2 178 232 T3 crystallized polymer, 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 percentages. by lower weight of crystallized polymer parts of the composition, the maximum dominant temperature will be 80<sup>°</sup>C (that is, the lowest of 80<sup>°</sup>Cy99<sup>°</sup>C) and the percentage by weight of the part of polymer crystallized at the maximum dominant 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 the polymerization of monoamers, 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 monoamers. The generic term "interpolymer" includes both 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 monamers).
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 wide short chain branching 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 comonoamer is randomly distributed within a given polymer molecule and in which substantially all of the molecules of polymer have the same molar ratio of ethylene to comonoamer. The term refers to an ethylene interpolymer characterized by a relatively high short chain branching distribution index (SCBDI) or composition distribution branching index (CDBI). That is, the interpolymer has a 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 portion of measurable high-density, high-crystallinity polymer and will still be 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 comonoomer 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 monoomer 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; ao 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 interpolymer monoomer distribution and SCBDI are determined using NMR (nuclear magnetic resonance) analysis. <sup>13</sup>C according to the techniques described in US Patent No. 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 the analytical temperature rise elution fractionation analysis (it is still described in US Patent Number 5,008,204 and abbreviated herein as "ATREF"),
ES 2 178 232 T3 composition to be analyzed is dissolved in a suitable hot solvent (for example, 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 called the short chain branching distribution (SCBD), as it indicates how the comonoomer (for example, octene) is uniformly distributed throughout the sample because as the elution temperature decreases, increases the comonoomer content.
The distribution of short chain branching 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. It will be appreciated by those skilled in the art 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 oven of an HP5800 II gas chromatograph. An electronic ooptic underdetector is used to measure the polymer concentration of the solution that remains at each sampling stage during the crystallization process. Reagent grade 1,2,4-trichloro-benzene 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.
The fractionation 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 / iiiinulo to 30 C. For compositions having densities below 0 , 89 g / cm<sup>3</sup>, topically CO 2 cryocooling is 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 container and the detector is flushed 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 polymers that remain on the filter. The containers 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. polymer. Specific integration of areas under maximum temperatures can quantify the amount of crystallizable polymer parts associated with specific maximum 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 curve of concentration versus temperature.
Specialists will appreciate that the level of precision for the separation by fractionation CRYSTAF is topically very high. That is, the determination of the percentage by weight at the maximum dominant temperature above 75 ° C is reproducible within ± 2 percentage points or ± less than 5% under the standard methods and procedures recommended by PolymerChar. 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, pages 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 maximum dominant temperature above 75 ° C, as determined using the fractionation technique for 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>
IS 2 178 232 T3 x 10<sup>(31,839 x composition density)</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 composition)</sup> with the density of the composition expressed in grams / cubic centimeter and less than or equal to 90, and mine preferably equal to or greater than the mathematical product <sub>1.7946 x 10</sub><sup>-28</sup> x 10<sup>(31.839x composition density)</sup> 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 the polymer crystallized at the maximum dominant temperature above 75<sup>°</sup>C, is then determined using a fractionation technique for analysis of crystallization in the range of 20 to 100<sup>°</sup>C, this is at least 10 percent, preferably at least 30 percent and more preferably at least 40 percent higher than the weight percent of part of polymer crystallized at the maximum dominant temperature above 75<sup>°</sup>C of a comparison composition that has essentially the same I2 and density of the composition.
By the phrase "essentially the same" is meant that the measured values for the I2 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 composition of comparison (not of the invention) they 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 expression "comparison composition" refers to any composition that does not fully meet the requirements defined for the composition of the invention (although it may have essentially the same I2 and composition density as the composition of the invention) that is compared with 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 composition of comparison can be deduced from said comparative determinations.
The composition density of the new composition is generally less than 0.945 g / cm<sup>3</sup>, preferably less than 0.935 g / cm<sup>3</sup> ymi preferably less than 0.93 g / cm<sup>3</sup>, and I am generally in the range from 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> ylomias especially in the range from 0.915 to 0.93 g / cm<sup>3</sup> (It is still 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<sup>°</sup>C / 2.16 kg (previously 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 interrelation is not linear. The overall melt index I2 of the new composition is in the range from 0.01 to 1000 g / 10 minutes, preferably greater than 0.1 g / 10 minutes in the range from 0.1 to 50, especially from 0.1 to 10, corn especially from 0.1 to 5 g / 10 minutes, and corn especially in the interval 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 at higher weights, such as, for example, common, ASTM D-1238, Condition 190.<sup>°</sup>C / 10 kg (previously known as "Condition N" and also known as I10). 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 I2 melt index values the mass flow ratio molten is conveniently designated I10 / I2. The new composition has a melt flow ratio I10 / I2 from 8 to 30. In specifically preferred embodiments, the I10 / I2 melt flow ratio is from 8 to 10.4 and especially from 8.2 to 10.3 and especially from 8.2 to 8.6.
The molecular weight distributions of ethylene polymers are determined by gel permeabilization 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-trichloro-benzene, 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
ES 2 178 232 T3 of 100 microliters.
The determination of the molecular weight with respect to the basic structure of the polymer is deduced by using polystyrene standards with narrow molecular weight distribution (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:
polyethylene = a * (Mpoii styrene) b.
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<sub>i</sub> (M<sup>j</sup> ))<sup>j</sup>; in which w<sub>i</sub> 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 more especially in the range from 4 to 7. However, when I10 / I2 is optimized, preferably the Mw / Mn is in the range of 4 to 4.5.
Parallel plate rheology can be conveniently used to predict ease of extrudability by indicating whether or not a particular ethylene interpolymer composition is shear thinned. In comparisons with known compositions having similar molecular weights and molecular weight distributions, Figure 12 indicates that the new composition has highly favorable parallel plate rheology. The manufacture 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 beginning of melt fracture and excellent melt strength. The excellent melt strength of the new composition results in excellent bubble stability during, for example, investigations for the manufacture of blown film.
Melt strength determinations are made at 190<sup>°</sup>C using a Goettfert Rheotens and an Instron capillary rheoometer. The capillary rheoometer was aligned and positioned above the Rheotens unit and supplied, 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 capillary nozzle of 2.1 mm diameter and 42 mm in length (L / D 20: 1) and supplies the filament to the take-up sprockets of the Rheotens unit rotating at 10 mm / 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 any convenient method, including dry mixing of the selected polymeric components together and subsequently melt mixing of the component polyomers in a mixer or by mixing the polymeric 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 stirring extruder employed directly downstream of a polymerization process).
Preferably, the new 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 the operations, the reactor configurations, catalytic 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 using more than two reactors. Most 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
ES 2 178 232 T3 a two-reactor system) with reactors configured in series, the polymer fraction is 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 polymer fraction in the first reactor will be less than 36 weight percent, especially less than 31 weight percent, and most especially less than or equal to 27 weight percent. The first reactor is a multiple reactor configuration (for example reactors arranged in series) that would topically be to that reactor located furthest 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 is used consisting of at least one recirculating flow closed-loop reactor and especially a polymerization system consisting of at least two non-operated recirculation closed-loop reactors. adiabatic 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 description of which is incorporated herein by reference.
Non-adiabaotic polymerization is preferably achieved at a volumetric thoracic 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 regime” as used here is the heat transfer coefficient of the procedure, U, in kW / square meter · ° K, multiplied by the heat exchange area, A, in square meters, of the device 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 inner or outer parameters of the procedure are used in terms of calculations and determinations of U and surface area. The calculations contained here are based on the areas of the external surfaces and the external diameters of the 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, may be used, including, for example, a cooling coil placed in a polymerization reactor or reactors, 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 which is designed as a heat exchange apparatus by providing cooling via a jacket or double pipe. 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 an outlet for the reactor flow stream and an inlet and an outlet for the transfer medium. toxic (e.g. water, water / glycol, water vapor, SYLTHERMO material or media<sup>TM</sup> supplied by The Dow Chemical Company under the designation DOWTHERM®). In another design, the reactor flow stream flows through a plurality of heat transfer tubes within the heat exchanger shell while the theoretical transfer medium flows over the outer surfaces of the tubes transferring the heat of reaction. or polymerization from the reactor flow stream. Alternatively, the reaction stream flows through the shell and the theoretical transfer medium flows through the tubes. Suitable heat exchange apparatus for use in the manufacture of the new composition are commercially available items (such as, for example, a Koch-supplied heat exchanger / stoat mixer) 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 useful olefin polymerization catalyst systems can be used to make the new composition including conventional ZieglerNatta-type catalyst systems, chromium catalyst systems, the so-called uonic site catalysts described, for example, polymerization of monocyclopentadienyl transition metal olefins described 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 catalytic systems (for example, as described by Stevens et al. 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
ES 2 178 232 T3 at least two reactors, preferably a conventional Ziegler-Natta type catalyst system is used 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 Patents No.<sup>you</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.
Particularly suitable organic magnesium compounds include, for example, hydrocarbon soluble dihydrocarbyl magnesiums such as dialkyl magnesiums and diaryl magnesiums. Examples of suitable dialkyl magnesium include particularly n-butyl-sec-butyl-magnesium, di-isopropylmagnesium, di-n-hexyl-magnesium, iso-propyl-n-butyl-magnesium, ethyl-n-hexyl-magnesium, ethyl- n-butyl-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 the active non-metal halides, the methyl halides, and hydrogen chloride.
Any method and procedure known in the art can be used to prepare a Ziegler-Natta type catalyst suitable for use in the present invention. A suitable method and procedure is described in US Patent No. 4,612,300, the disclosure of which is incorporated herein by reference (Example P). The described method and procedure involves sequentially adding Isopar hydrocarbon to a volume.<sup>TM</sup> E, a suspension of anhydrous magnesium chloride in Isopar hydrocarbon<sup>TM</sup>, a solution of EtAlCl2 in n-hexane, and a solution of Ti (O-iPr) 4 in Isopar hydrocarbon<sup>TM</sup>, 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 are 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 monoimers, conjugated or unconjugated dienes, polyenes, etc. Examples of such monomers include α-olefins C<sub>3</sub>-C<sub>20</sub> such as propylene, isobutylene, 1-butene, 1-hexene, 1pentene, 4-methyl-1-pentene, 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, tetrafluoroethylene, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and cycloalkenes, eg, cyclopentene, cyclohexene, and cyclooctene.
Additives, such as antioxidants (for example hindered phenolic compounds) such as IRGANOX<sup>TM</sup> 1010 heard the IRGANOX<sup>TM</sup> 1075 supplied by Ciba Geigy, phosphites (for example IRGAFOS<sup>TM</sup> 168 also supplied by Ciba Geigy, adhesion additives (for example PIB), SANDOSTAB PEPQ<sup>TM</sup> (supplied by Sandoz), pigments, colorants, fillers, antistatic agents, treatment 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 anti-stick, mold release, and coefficient of friction characteristics including, but not limited to, silicon dioxide. treated 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 (EAA) copolymers or other functional polyomers, 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, the high-strength packaging of electroinically sensitive items.
The manufactured articles of the invention (such as, for example, but not limited to, films, layer
ES 2 178 232 T3 for films, fibers, molded articles and coatings) may also include recycle and waste materials and diluent polyomers, as long as the properties of processibility, impact resistance and tear resistance are balanced. Examples of diluent materials include, for example, anhydride modified elastoomers, rubbers and 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 interpolymer (EAA), ethylene / vinyl acetate interpolymer (EVA), and ethylene / methyl methacrylate interpolymer (EMA), and combinations thereof.
The fabricated articles 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 retroactive film and barrier retroactive applications; containers and packagings formed by form / fill / seal machinery; peelable sealable container and packaging structures; containers for cooked food; compression filled containers; film for hermetically sealed 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 where lower levels are now possible high 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, it is appreciated by those skilled in the art 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, inventive compositions 1 and 2 were manufactured using a non-adiabaotic 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 No. 5,370,940 using an adiabaotic polymerization system consisting of two spheric 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 used in the manufacture of comparative compositions 1 and 2, except that a catalytic system with a built-in geometry was used in an Rx1 closed-loop flow reactor. instead of a heterogeneous Ziegler-Natta type titanium coordination catalytic system.
IS 2 178 232 T3
TABLE 1
<td colspan="3">Invention Example 1</td><td colspan="2">Example 2 of the Invention</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>Procedure temperature, ◦C</td><td> 161</td><td> 190</td><td> 161</td><td> 190</td>
<td>Process pressure, kPa gauge</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>C conversion<sub>2</sub>, % (global)</td><td> 73,6</td><td> 89,3 (92,4)</td><td> 73,5</td><td> 90 (92,9)</td>
<td>Solvent / C feed ratio<sub>2</sub></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>C flow<sub>8</sub> of new contribution (kg / h)</td><td> 0</td><td> 8,6</td><td> 7,8</td><td> 0</td>
<td>Pure hydrogen flow, 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>
IS 2 178 232 T3
TABLE 1 Continued
<td colspan="3">Example 1 of the Invention</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 Ziegler-Natta type titanium coordination catalytic system</td><td>Heterogeneous Ziegler-Natta type titanium catahotic coordination system</td><td>Heterogeneous Ziegler-Natta type titanium catahotic coordination system</td><td>Heterogeneous Ziegler-Natta type titanium catahotic coordination 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 heat separation intensity (kW / m<sup>3</sup>. ° K)</td><td> - 18,5</td><td> 11,5</td><td> - 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>
TABLE 2
<td colspan="3">Comparative Example 3</td>
<td></td><td>Rx1 spherical</td><td>Rx2 spherical</td>
<td>Procedure temperature, ° C</td><td> 159</td><td> 197</td>
<td>Polymer concentration,% by weight</td><td> 6,7</td><td> 12,2</td>
<td>C conversion<sub>2</sub>, % (global)</td><td> 80</td><td> 90,5 (92,9)</td>
<td>Solvent / C feed ratio<sub>2</sub></td><td> 13</td><td> 5,36</td>
<td>Solvent flow (kg / h)</td><td> 57,057</td><td> 52,716</td>
IS 2 178 232 T3
TABLE 2 Continued
<td colspan="3">Comparative Example 3</td>
<td></td><td>Rx1 spherical</td><td>Rx2 spherical</td>
<td>C flow<sub>2</sub> (kg / h)</td><td> 4389</td><td> 9854</td>
<td>C flow<sub>8</sub> of new contribution (kg / h)</td><td> 1100</td><td></td>
<td>Pure hydrogen flow, 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>
<td>Catalyst type</td><td>Heterogeneous Ziegler-Natta type titanium coordination catalytic system</td><td>Heterogeneous Ziegler-Natta 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 T3
With respect to the polymerization system used to make compositions 1 and 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 finished product. The independent control of polymer concentration and process temperature that is characteristic of non-adiabaitic recirculating flow closed loop reactors proves to be of tremendous economic benefit with respect to the requirements for good gel quality, particularly at Lowest flow rates of the product.
The nominal 0.025 millimeter blown film was manufactured from compositions 1 and 2 of the invention and from 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>Example 1 of the invention</td><td>Example 2 of the invention</td><td>Example comparative 3</td><td>Example comparative 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>Line height</td><td></td><td></td><td></td><td></td>
<td>crystallization (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>Blow ratio</td><td> 2,7</td><td> 2,7</td><td> 2,7</td><td> 2,7</td>
In actual blown film manufacture Compositions 1 and 2 of the invention and Comparative Composition 3 exhibited good processibility and excellent melt stability as indicated by relatively high production yields and line heights. relatively low crystallization (ie good bubble formation stability), respectively. Conversely, comparative composition 4 exhibited a relatively low production yield and a relatively high crystallization line height.
Table 4 lists some physical properties and performance properties of the film for compositions 1 and 2 of the invention and comparative compositions 3 and 4.
Table 4 indicates that compositions 1 and 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 compositions 1 and 2 of the invention was 33-46 percent and 34-37 percent, respectively, higher than the tear strength of comparative composition 4.
TABLE 4
<td>Example</td><td>Example 1 of the invention</td><td>Example 2 of the invention</td><td>Example comparative 3</td><td>Example comparative 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>I<sub>2</sub> g / 10 minutes</td><td> 0,44</td><td> 0,42</td><td> 0,55</td><td> 0,54</td>
<td>I<sub>10</sub> g / 10 minutes</td><td> 4,51</td><td> 3,96</td><td> 5,01</td><td> 3,77</td>
<td><sup>I</sup>10<sup>/ I</sup>2</td><td> 10,45</td><td> 9,47</td><td> 9,03</td><td> 6,98</td>
<td>M<sub>w</sub>/ 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>
IS 2 178 232 T3
TABLE 4 Continued
<td>Example</td><td>Example 1 of the invention</td><td>Example 2 of the invention</td><td>Example comparative 3</td><td>Example comparative 4</td>
<td>Number average molecular weight</td><td> 36000</td><td> 32200</td><td> 30600</td><td> 52200</td>
<td>Melt strength</td><td></td><td></td><td></td><td></td>
<td>Rheotens, 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 standardized at a thickness of 25 mm.
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 Compositions 7-10 of the invention.
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.
Compositions 7-10 of the invention were manufactured using the same polymerization system described above as used to manufacture compositions 1 and 2 of the invention. The process conditions used for compositions 7-10 of the invention were essentially similar to those used for compositions 1 and 2 of the invention except that the flux of fresh octene was higher for compositions 7-10 of the invention. and the fresh hydrogen fluxes to each reactor were adjusted to provide higher I10 / I2 ratios for compositions 7-10 of the invention. Composition 7 of the invention was manufactured using a 30 weight percent polymer fraction in the Rx1 reactor (ie, the first reactor). Compositions 8-10 of the invention 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 phasic 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><sup>I</sup>10<sup>,</sup>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>Example 1 of the invention</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>
IS 2 178 232 T3
TABLE 5 Continued
<td>Example</td><td>Density g / cm<sup>3</sup></td><td>I2, g / 10 min.</td><td><sup>I</sup>10<sup>,</sup>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 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>Example 7 of the invention</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>Example 8 of the invention</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>Example 9 of the invention</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>Example 10 of the invention</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 crystallized polymer at the maximum dominant temperature above 75<sup>°</sup>C as a function of composition density for compositions of the invention and comparative compositions, was generated using the data in Table 5. Using the crystallization data for compositions 1 and 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 part of polymer crystallized at temperature. dominant maximum above 75<sup>°</sup>C for the respective compositions. Figure 24 shows with respect to tear strength behavior that there is an apparent optimum at about 75 weight percent for the crystallized polymer portion at the maximum dominant temperature above 75<sup>°</sup>C.
ATREF was performed for compositions 1 and 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 global composition densities the compositions of the invention possess more polymer that crystallizes at higher temperatures, and this distinction becomes even more prominent at higher equivalent composition 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 results of Mv.
GPC raw molecular data for compositions 1 and 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 T3
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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 compositions of the invention and comparative composition 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 percent by weight 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 the examples of the invention. 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 a higher uniformity of composition to compensate for the lower molecular weight and still achieve excellent tear resistance of the film and therefore ultra-high molecular weights are not required to obtain excellent tear resistance of blown film.
In another evaluation, the effect on the I10 / I2 product and the specific variations of the procedure were investigated at a nominal composition density of 0.918 g / cm<sup>3</sup>. In this evaluation, composition 9 of the invention was compared with four other compositions of the invention, compositions 11-14 of the invention. Compositions 11-14 of the invention were manufactured using essentially the same polymerization system as described hereinabove for the composition2 of the invention. While the fresh comonoomer (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 fraction of the weight percent of the production. of polymer between the first and second reactors as well as a variation in terms of the injection of the catalytic system and the feed (that is, the ethylene and the newly supplied 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 fresh feed using a mechaonic stirrer (i.e., a lightening mixer) and Figure 27 shows the separate injection of the Ziegler-Natta catalyst system and the feed of new contribution as well as two injection points of the feeding of new contribution.
A nominal 0.02mm blown film was manufactured from the compositions of the invention 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 of the invention exhibit a better balance of properties over compositions 9 and 11 of the invention, and thus compositions 12-14 of the invention represent especially preferred embodiments herein. invention. This product preference is attributed to a combination of product and process or system preferences since Table 7 indicates that compositions 12-14 of the invention 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 catalytic system and the feed back as opposed to simultaneous introduction (such as, for example, as in composition 9 of the invention in which the catalyst and the fresh feed are injected together and mixed with the contents of the reaction stream in a mechaonic mixer) or the previous mixture of the catalytic system and fed it again input.
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 (pure) 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 procedure, 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 pipes and equipment) and the speed of the reaction current. Most preferably, in the present invention, the delay in the injection time or the contacting time is preferably at least 2 seconds and most preferably at least 5 seconds.
IS 2 178 232 T3
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, staotic mixers are employed at the various injection sites; that is, injection is achieved without the use of a mechaonic mixer or stirring devices. Also, preferably, the polymerization system is provided with at least two separate feed injection points (multiple injection points) in at least one reactor.
TABLE 7
<td>Example</td><td>Density of the composition</td><td>I2, g / 10 min.</td><td>I10 / I2</td><td>Fraction of polymer *</td><td>New contribution from comonomer to reactor No.</td><td>Mixer at the injection point</td><td>Tearing MD Elmendorf, g / mm</td><td>Impact for dart, grams</td>
<td>Example 9 of the invention</td><td> 0,9188</td><td> 0,5</td><td> 10,32</td><td> 25,6</td><td> 1</td><td>Mechanical</td><td> 20039</td><td> 250</td>
<td>Example 11 of the invention</td><td> 0,9182</td><td> 0,54</td><td> 10,63</td><td> 37</td><td> 1</td><td>Static</td><td> 23780</td><td> 312</td>
<td>Example 12 of the invention</td><td> 0,918</td><td> 0,48</td><td> 8,38</td><td> 30,5</td><td> 1</td><td>Static</td><td> 17677</td><td> > 850</td>
<td>Example 13 of the invention</td><td> 0,9182</td><td> 0,51</td><td> 10,17</td><td> 30,7</td><td> 1</td><td>Estotic</td><td> 19252</td><td> 620</td>
<td>Example 14 of the invention</td><td> 0,9179</td><td> 0,47</td><td> 10,18</td><td> 25,6</td><td> 1</td><td>Estotic</td><td> 23543</td><td> 722</td>
MD Elmendorf tear was measured as Type B and determined in accordance with ASTM D1922. Impact per dart was measured as Method A and determined in accordance with ASTM D1709.
* Polymer fraction refers to the percentage by weight of polymer production that took place in the first reactor of the two-reactor polymerization system used to make the compositions of the invention.
In another evaluation, the effect on the I10 / I2 product and the specific variations of the procedure were investigated at a nominal compositional density of 0.927 g / cm<sup>3</sup>. In this evaluation, compositions 1 and 2 of the invention were compared with composition 15 of the invention. Composition 15 of the invention was manufactured using essentially the same polymerization system as described above for Composition 2 of the invention. Kenix static mixers were used at the various injection sites as shown in Figure 27 for all of the three compositions of the invention. Table 8 shows that the fraction of the polymer 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 comonoomer injected into the second reactor as opposed to the first reactor.
A nominal 0.08mm blown film was manufactured from these inventive compositions using a Macro blown film unit equipped with a 15.2cm annular die at a die pitch of 1mm. The density, I2, I10 / I2 as well as the tear and impact behavior of the various compositions were measured and are also reported in Table 8.
IS 2 178 232 T3
TABLE 8
<td>Example</td><td>Density of the composition</td><td>I2, g / 10 min.</td><td>I10 / I2</td><td>Fraction of polymer *</td><td>New contribution from comonomer to reactor No.</td><td>Mixer at the injection point</td><td>Tearing MD Elmendorf, g / mm</td><td>Impact for dart, grams</td>
<td>Example 1 of the invention</td><td> 0,927</td><td> 0,46</td><td> 10,46</td><td> 30,4</td><td> 2</td><td>static</td><td> 9488</td><td> 313</td>
<td>Example 2 of the invention</td><td> 0,9274</td><td> 0,39</td><td> 10,25</td><td> 30,3</td><td> 1</td><td>static</td><td> 10394</td><td> 457</td>
<td>Example 15 of the invention</td><td> 0,9275</td><td> 0,5</td><td> 11,67</td><td> 30,3</td><td> 1</td><td>static</td><td> 9685</td><td> 394</td>
MD Elmendorf tear was measured as Type B and determined in accordance with ASTM D1922. Impact per dart was measured as Method A and determined in accordance with ASTM D1709.
* Polymer fraction refers to weight percent of polymer production that took place in the first reactor of the two-reactor polymerization system used to make the compositions of the invention.
With respect to compositions 1 and 15 of the invention, Table 8 shows that composition 2 of the invention exhibits a better balance of properties, and therefore (like compositions 12-14 of the previous invention) composition 2 of the invention. 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 feeding of fresh supply and (3) feeding of fresh (pure) comonoomer in the first reactor (as opposed to I10 / I2 ratios greater than 10.4 for both compositions 1 and 15 of the invention as to the injection of fresh comonomer in the second reactor as regards composition 1 of the invention). Therefore, in especially preferred embodiments, the fresh comonoomer is initially injected separately into the polymerization system, for example, but not limited to, 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 onyx of flow and of the conversion of ethylene in percentage of the process 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 of the invention were manufactured using essentially the same polymerization system as described above for composition 12 of the invention. In particular, staotic mixers were used and the new comonoomer 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, Hydrogen flux in each reactor was controlled to provide the onyx and I10 / I2 values listed per sample in Table 9 and the polymer fraction in the first reactor was as indicated per sample in Table 9. The percent ethylene conversion in the first reactor was varied by known techniques (for example, by controlling the rate of feeding the catalyst to the reaction stream).
A nominal 0.08mm blown film was made from these compositions of the invention using a Macro blown film unit equipped with a 15.2cm 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 performance and impact properties of Composition 16-19 of the invention as compared to Composition 12 of the invention.
IS 2 178 232 T3
TABLE 9
<td>Example</td><td>Density of the compo- sition</td><td>I2, g / 10 min.</td><td>I10 / I2</td><td>Tails- tion of cop- Mere*</td><td>Conversion of C2 in percentage cut</td><td>Mw / Mn</td><td>critical ^</td><td>'^^ rned ^^'</td><td>Tdpt for on from 75 ^ C</td><td>MD Elmendorf tear, g / mm</td><td>Impact for dart, grams</td>
<td>Example 12 of the invention</td><td> 0,9180</td><td> 0,48</td><td> 8,38</td><td> 30,5</td><td> 75</td><td> > 4</td><td> 30,4</td><td> 36,1</td><td> 81,4</td><td> 17677</td><td> 742</td>
<td>Example 16 of the invention</td><td> 0,9183</td><td> 0,48</td><td> 8,39</td><td> 25,7</td><td> 76</td><td> 4,0</td><td> 31,0</td><td> 32,4</td><td> 80,8</td><td> 14331</td><td> 816</td>
<td>Example 17 of the invention</td><td> 0,9156</td><td> 0,50</td><td> 8,06</td><td> 25,6</td><td> 76</td><td> 4,1</td><td> 25,5</td><td> 28,3</td><td> 80,8</td><td> 18701</td><td> 924</td>
<td>Example 18 of the invention</td><td> 0,9185</td><td> 0,44</td><td> 8,10</td><td> 25,6</td><td> 89</td><td> 4,1</td><td> 31,5</td><td> 35,9</td><td> 80,4</td><td> 17992</td><td> 897</td>
<td>Example 19 of the invention</td><td> 0,9175</td><td> 0,72</td><td> 8,33</td><td> 25,7</td><td> 89</td><td> 4,2</td><td> 29,3</td><td> 30,2</td><td> 80,9</td><td> 19094</td><td> 1004</td>
The MD Elmendorf tear was measured as Type B and determined in accordance with ASTM D1922.
The impact per dart was measured using a modification of ASTM D1709 Method A (ie the distance of the dart path after the film break was increased to 61 cm and the total weight was increased to 1500 grams).
* Polymer fraction refers to weight percent of polymer production that took place in the first reactor of the two-reactor polymerization system used to make the compositions of the invention.
t W <sub>critical</sub> denotes the percentage by weight of the crystallized polymer parts at the maximum dominant temperature above 75<sup>°</sup>C is calculated from the equation 1.7946 x 10 (<sup>31,839 x</sup> composition density) where the density of the composition is in grams / cubic centimeter and the maximum dominant temperature is determined using the fractionation technique for analysis of crystallization through the range of 20 to 100<sup>°</sup>C.
tt Wmeasured denotes the percentage by weight of the crystallized polymer parts at the maximum dominant temperature above 75<sup>°</sup>C, is then determined using the fractionation technique for the analysis of crystallization in the range of 20 to 100<sup>°</sup>C.
The results in Table 9 show that the composition 19 of the invention exhibits an outstanding balance of properties, as it surprisingly had the highest tear resistance and impact resistance of all the samples evaluated even though its melt index was relatively high. 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 injection separated from the catalytic system and the fresh feed and by injecting the fresh feed (pure) comonomer feed into the first reactor, This embodiment, the most preferred 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 percent by weight) and to be controlled
ES 2 178 232 T3 the weight percent of the comonoomer 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 more preferably greater than or equal to 87 percent by weight).
Contents33
41 sheets
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29 members in 18 offices
Priority claims14
| Document | Office | Kind | Date |
|---|---|---|---|
| 19970053263P | United States of America | – | |
| 5326397 | United States of America | P | |
| 5326397 | United States of America | P | |
| 19970063390P | United States of America | – | |
| 6339097 | United States of America | P | |
| 6339097 | United States of America | P | |
| 1998US13854 | World Intellectual Property Organization (WIPO) | – | |
| 9813854 | United States of America | W | |
| 9813854 | United States of America | W | |
| 53263P | – | – | – |
| 63390P | – | – | – |
| 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 | |
| ES2178232T3This record | Spain | T3 | |
| DE69807702T2 | Germany | T2 | |
| CA2296635C | Canada | C | |
| EP0996651B2 | European Patent Office (EPO) | B2 | |
| ES2178232T5 | 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 INTERPOLÍMERAS DE ETILENO DE AMPLIA DISTRIBUCIÓN DE PESOS MOLECULARES Y COMPOSICIÓN UNIFORME, PROCEDIMIENTO PARA SU FABRICACIÓN Y ARTÍCULOS PRODUCIDOS CON ELLAS.
- English
- INTERPOLYMER ETHYLENE COMPOSITIONS OF WIDE DISTRIBUTION OF MOLECULAR WEIGHTS AND UNIFORM COMPOSITION, PROCEDURE FOR ITS MANUFACTURE 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
- B01J8 00
- B01J19 24
- B29C55 28
- B29K23 00
- B29L7 00
- B29L9 00
- B32B27 32
- C08F2 01
- C08F10 02
- C08F110 02
- C08F210 16
- C08J5 18
- C08L23 04