CN115413281B - Polyethylene composition for film layer - Google Patents

Polyethylene composition for film layer Download PDF

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CN115413281B
CN115413281B CN202180023561.1A CN202180023561A CN115413281B CN 115413281 B CN115413281 B CN 115413281B CN 202180023561 A CN202180023561 A CN 202180023561A CN 115413281 B CN115413281 B CN 115413281B
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polymer
ethylene
polymer composition
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mfr
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CN115413281A (en
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约翰·贾米森
莱文德拉·图佩
保利·莱斯基宁
贾莫·凯拉
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Borealis AG
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Abstract

The present invention relates to a polymer composition, the use of said polymer composition in film applications and a film comprising the polymer composition of the invention.

Description

Polyethylene composition for film layer
Technical Field
The present invention relates to a polymer composition, the use of said polymer composition in film applications and a film comprising the polymer composition of the invention.
Background
Unimodal Polyethylene (PE) polymers, such as SSC products, are commonly used in film applications. Unimodal PE polymers have e.g. good optical properties, such as low haze, but for example, melt processing of such polymers is not satisfactory in terms of production and may also lead to quality problems of the final product. Multimodal PE polymers with two or more different polymer components are better processed, but melt homogenization of for example multimodal PE may be problematic, leading to inhomogeneities in the final product, which is indicated by a high gel content of the final product.
EP 1472298A of nordic chemical company (Borealis) discloses a multimodal PE polymer composition with two different comonomers. The multimodal PE polymer is polymerized in the presence of a metallocene catalyst. Examples disclose multimodal PE polymers having two polymer components with, for example, different types of comonomers.
The disclosure does seem to define the melt flow of the final multimodal PE polymerKinetic ratio MFR 21 /MFR 2 (FRR 21/2 ) But the melt flow ratio of the exemplary polymers varies in the range of 38-55. EP 1472298 does not mention any sealing properties of the final multimodal PE polymer.
There is a continuing need to find multimodal PE polymers with different property balances to provide tailored solutions to meet the increasing demands of end-use manufacturers, e.g. to reduce production costs, while maintaining or even improving the properties of the final product. There is also a need for tailored polymer solutions to meet the equipment specifications that continue to evolve in the end-use field.
Disclosure of Invention
The present invention relates to a polymer composition comprising
80.0-99.0 wt%, based on the total weight of the polymer composition, (1) a multimodal polymer of ethylene with at least two different comonomers selected from alpha-olefins having 4 to 10 carbon atoms,
the multimodal polymer of ethylene has the following properties
a)MFR 2 From 0.5 to 10g/10min (according to ISO 1133, at 190℃and under a load of 2.16 kg),
b)MFR 21 /MFR 2 is from 13 to 35 (MFR) 21 At 190℃and 21.6kg load) and
c) Mw/Mn is 5 or less; and
The multimodal polymer of ethylene comprises at least
Ethylene Polymer Components (A) and
an ethylene polymer component (B),
whereby the MFR of the ethylene polymer component (A) 2 MFR different from the ethylene polymer component (B) 2 And (b)
Whereby the multimodal polymer of ethylene (1) is further multimodal in terms of density, the density of the ethylene polymer component (A) being higher than the density of the ethylene polymer component (B)>41kg/m 3 ，
And 1.0 to 20.0 weight percent of (2) LDPE based on the total weight of the polymer composition.
The term "multimodal" in the context of the polymer of ethylene (1) refers herein to multimodal with respect to the Melt Flow Rate (MFR) of the ethylene polymer components (a) and (B), i.e. the ethylene polymer components (a) and (B) have different MFR values. The multimodal polymer of ethylene (1) may have other multimodal properties with respect to one or more other properties between the ethylene polymer components (a) and (B), as will be described below.
The polymer composition of the present invention as defined above, below or in the claims is also referred to herein simply as "polymer composition".
The "(1) multimodal polymer of ethylene with at least two different comonomers selected from alpha-olefins having 4 to 10 carbon atoms" or "multimodal polymer of ethylene (1)" as defined above, hereinafter or in the claims, respectively, is also referred to herein simply as "polymer of ethylene".
When referring to both the ethylene polymer component (a) and the ethylene polymer component (B), it is also referred to as "ethylene polymer components (a) and (B)".
Unexpectedly, the polymer compositions of the present invention provide improved sealing properties, such as low Seal Initiation Temperature (SIT) and/or improved optical properties, such as improved haze and/or gloss. Furthermore, (1) the SIT of the multimodal polymer of ethylene can surprisingly be changed/modified preferably without the addition of LDPE (2).
The invention also relates to a film comprising at least one layer comprising said polymer composition. The film may be a single layer film comprising a polymer composition or a multilayer film wherein at least one layer comprises the polymer composition. The terms "monolayer film" and "multilayer film" have well known meanings in the art.
The following preferred embodiments, properties and subgroups of the polymer composition, the polymer of ethylene (1) and its ethylene polymer components (a) and (B) and the films of the present invention including their preferred ranges are independently generalizable so that they can be used in any order or combination to further define the preferred embodiments of the polymer compositions and articles of the present invention.
Polymer composition, ethylene Polymer (1) and LDPE (2), and ethylene Polymer component (A) and ethylene Polymer component (B)
As mentioned above, the polymer of ethylene (1) is referred to herein as "multimodal" because the ethylene polymer component (a) and the ethylene polymer component (B) are produced under different polymerization conditions resulting in different melt flow rates (MFR, e.g. MFR 2 ). That is, the polymer composition is multimodal with respect to at least the difference in MFR of the two ethylene polymer components (a) and (B). The term "poly" includes a "bimodal" composition consisting of two components having a difference in the MFR.
Preferably, the MFR of the ethylene polymer component (A) 2 From 1 to 50g/10min, preferably from 1 to 40, more preferably from 1 to 30, more preferably from 2 to 20, more preferably from 2 to 15, even more preferably from 2 to 10, g/10min. More preferably, the ethylene polymer component (A) has a higher MFR than the ethylene polymer component (B) 2 。
In one embodiment, the amount of (1) may preferably be between 85.0 and 99.0 wt%, more preferably in the range > 85.0 and 95.0 wt%, and the amount of (2) may thus preferably be between 1.0 and 15.0 wt%, preferably between 5.0 and <15.0 wt%.
Even more preferably, the MFR of the ethylene polymer component (A) 2 MFR of multimodal polymer (1) with final ethylene 2 The ratio is in the range of 1.0 to 50, preferably 1.5 to 40, more preferably 1.8 to 30, even more preferably 2.0 to 25, such as 2.0 to 10.
Preferably, the MFR of polymer (1) of ethylene 2 From 0.5 to 7.0, more preferably from 0.5 to 5.0g/10min. Preferably, the MFR of polymer (1) of ethylene 21 /MFR 2 From 13 to 30, more preferably from 15 to 30, even more preferably from 15 to 25.
If the ethylene polymer component, e.g. component (B), has MFR 2 As they cannot be separated from the mixture of at least the ethylene polymer components (A) or (B) and cannot be measured, so-called "can be usedEquation (+)>Polymer processing society, european/African regional conference, goderburg, sweden, 1997, 8, 19-21 days (++)>The Polymer Processing Society, europe/Africa Region Meeting, gothenburg, sweden, august 19-21,1997)) by:
according to the describedIn the equation (eq.3), for MFR 2 A=5.2 and b=0.7. In addition, w is the weight fraction of other ethylene polymer components having a higher MFR, e.g. component (a). The ethylene polymer component (a) can thus be regarded as component 1 and the ethylene polymer component (B) as component 2.MI (MI) b MFR of Polymer (1) which is the final ethylene 2 . When the MFR of the ethylene polymer component (A) 1 (MI 1 ) And finally a polymer (1) of ethylene (MI b ) When known, the MFR of the ethylene polymer component (B) 2 (MI 2 ) Can be solved from equation 1.
The at least two alpha-olefin comonomers of the polymer (1) of ethylene having from 4 to 10 carbon atoms are preferably 1-butene and 1-hexene.
Naturally, in addition to the multimodal nature (i.e. the difference between the two) regarding the MFR of the ethylene polymer components (a) and (B), the polymer (1) of ethylene of the polymer composition of the invention may also be multimodal, for example regarding one or both of the other two properties:
with respect to the following multimodal, i.e. the difference between the two,
-the type or comonomer content of the comonomer present in the ethylene polymer components (a) and (B), or the type and content of the comonomer present in the ethylene polymer components (a) and (B); and/or
-density of the ethylene polymer components (a) and (B).
Preferably the multimodal polymer (1) of ethylene of the polymer composition is further multimodal in terms of comonomer type and/or comonomer content (mole%), preferably the alpha olefin comonomer of ethylene polymer component (a) having 4 to 10 carbon atoms is different from the alpha olefin comonomer of ethylene polymer component (B) having 4 to 10 carbon atoms, preferably the alpha olefin comonomer of ethylene polymer component (a) having 4 to 10 carbon atoms is 1-butene and the alpha olefin comonomer of ethylene polymer component (B) having 4 to 10 carbon atoms is 1-hexene.
Preferably the ratio of [ the amount (mole%) of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) ] to [ the amount (mole%) of at least two alpha olefin comonomers having 4 to 10 carbon atoms of the final multimodal polymer of ethylene (1) ] is from 0.1 to 0.6, preferably from 0.1 to 0.4, more preferably the amount (mole%) of comonomer of the ethylene polymer component (a) is lower than the amount (mole%) of comonomer of the ethylene polymer component (B).
The comonomer content of components (a) and (B) may be measured, or, if and preferably, in a so-called multistage process, one of the components is first formed, then the other is formed in the presence of the first formed component, the comonomer content of the first formed component, for example component (a), may be measured, and the comonomer content of the other component, for example the comonomer content of component (B), may be calculated as follows:
comonomer content in component B (% by mole) = (comonomer content in final product (% by mole) - (weight fraction of component a)/(comonomer content in component a (% by mole)))/(weight fraction of component B)
Preferably, the amount (mole%) of the alpha-olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) is 0.03 to 5.0 mole%, preferably 0.05 to 4.0 mole%, more preferably 0.1 to 3.0 mole%, even more preferably 0.1 to 2.0 mole%, more preferably 0.15 to 1.5 mole%, even more preferably 0.15 to 1.0 mole%.
In one embodiment, the amount (mole%) of alpha olefin comonomer, preferably 1-hexene, having from 4 to 10 carbon atoms present in the ethylene polymer component (B) may be from 0.3 to 10.0 mole%, preferably from 0.5 to 9.0 mole%, more preferably from 1.0 to 8.5, even more preferably from 3.0 to 8.0 mole%.
More preferably, the total amount of comonomer present in the multimodal polymer of ethylene (1) is from 0.5 to 10 mole%, preferably from 1.0 to 8 mole%, more preferably from 1.0 to 5 mole%, more preferably from 1.5 to 5.0 mole%.
Further specific multimodal, i.e. the difference between the comonomer type and comonomer content between the ethylene polymer component (a) and the ethylene polymer component (B), further contributes to very advantageous sealing properties, e.g. an excellent seal initiation temperature can be achieved even at low temperatures. In addition, optical characteristics such as haze are also at an advantageous level.
Even more preferably, the multimodal polymer of ethylene (1) of the polymer composition is multimodal further with respect to the density difference between the ethylene polymer component (a) and the ethylene polymer component (B). The density of the ethylene polymer component (A) is higher than that of the ethylene polymer component (B), i.e.higher than 41kg/m 3 Further preferably a height of > 42 or 42.5kg/m 3 . More preferably, the ethylene polymer component (A) has a density of 925 to 950, preferably 930 to 945kg/m 3 And/or the ethylene polymer component (B) has a density of 880 to < 910, preferably 890 to 905kg/m 3 。
The multimodal polymer of ethylene (1) is preferably a Linear Low Density Polyethylene (LLDPE) having a known meaning. Even more preferably, the multimodal polymer (1) of ethylene, preferably of the polymer composition, has a density of 910 to 935, preferably 912 to 925kg/m 3 。
The multimodal nature with respect to density further contributes to the beneficial mechanical properties of the polymer composition.
Furthermore, the polymer (1) of ethylene of the polymer composition may also be multimodal with respect to the (weight average) molecular weight of the ethylene polymer components (a) and (B), i.e. there is a difference between the two. Multimodal re weight average molecular weight refers to the form of the molecular weight distribution curve of such multimodal polyethylene, i.e. the appearance of a graph of the polymer weight fraction as a function of its molecular weight will show two or more maxima or at least be significantly broadened compared with the curve of the individual components.
More preferably, the multimodal polymer of ethylene (1) is as defined above, below or in the claims including any preferred range or embodiment of the polymer composition, at least with respect to the MFR of the ethylene polymer component (a) and the ethylene polymer component (B) 2 The comonomer type and comonomer content (mol%) are multimodal, i.e. have a difference between them, and the density with respect to the ethylene polymer component (a) and the ethylene polymer component (B) are multimodal, i.e. have a difference between them.
Most preferably, the polymer composition of the invention comprises a multimodal polymer of ethylene (1) comprising, preferably consisting of, ethylene polymer component (a) and ethylene polymer component (B), as defined above, below or in the claims, wherein
MFR of ethylene Polymer component (A) 2 MFR higher than the ethylene polymer component (B) 2 ；
More preferably, the MFR of the ethylene polymer component (A) 2 1.0 to 50g/10min, preferably 1.0 to 40g/10min, more preferably 1.0 to 30g/10min, more preferably 2.0 to 20g/10min, more preferably 2.0 to 15g/10min, even more preferably 2.0 to 10g/10min;
even more preferably, the MFR of the ethylene polymer component (a) 2 MFR of multimodal polymer (1) with final ethylene 2 The ratio is 1 to 50, preferably 1.5 to 40, preferably 1.8 to 30, more preferably 2.0 to 25, more preferably 2 to 10;
and wherein
The ethylene polymer component (a) has a different comonomer than the ethylene polymer (B);
More preferably, the ethylene polymer component (a) has a lower amount (mole%) of comonomer than the ethylene polymer component (B), even more preferably the ratio of [ the amount (mole%) of alpha olefin comonomer of comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) ] to [ the amount (mole%) of at least two alpha olefin comonomers having 4 to 10 carbon atoms of the final multimodal polymer of ethylene (1) ] is 0.1 to 0.6, preferably 0.1 to 0.4;
even more preferably, wherein the alpha-olefin comonomer having 4 to 10 carbon atoms of the ethylene polymer component (a) is 1-butene and the alpha-olefin comonomer having 4 to 10 carbon atoms of the ethylene polymer component (B) is 1-hexene;
and wherein
The density of the ethylene polymer component (a) is higher than the density of the ethylene polymer component (B);
more preferably, the multimodal polymer (1) of ethylene, preferably of the polymer composition, has a density of 910 to 935kg/m 3 Preferably 912-925kg/m 3 ；
Even more preferably, the ethylene polymer component (A) has a density of 925 to 950kg/m 3 Preferably 930-945kg/m 3 。
In one embodiment, the multimodal polymer of ethylene (1) has a Mw/Mn of between 2.5 and 4.8, preferably between 3.0 and < 4.5, more preferably between 3.5 and 4.2.
In further embodiments, the polymer compositions of (1) and (2) may have a Seal Initiation Temperature (SIT) as determined in the experimental section that is equal to or within plus or minus 2.5 ℃ of the SIT of (1), and/or the polymer compositions of (1) and (2) may have a SIT between 55 ℃ and 90 ℃, preferably between 60 ℃ and 80 ℃, further preferably between 62 ℃ and 75 ℃, further preferably between >62 ℃ and 70 ℃.
Preferably, the multimodal polymer of ethylene (1) comprises the ethylene polymer component (a) in an amount of from 30 to 70 wt%, preferably from 32 to 60 wt%, more preferably from 35 to 55 wt%, even more preferably from 40 to 50 wt%, and the ethylene polymer component (B) in an amount of from 70 to 30 wt%, preferably from 68 to 40 wt%, more preferably from 45 to 65 wt%, more preferably from 50 to 60 wt%, based on the total amount (100 wt%) of the polymer of ethylene (1). Most preferably, the polymer of ethylene (1) consists of ethylene polymer components (a) and (B) as the sole polymer components. Thus, the ratio between the ethylene polymer component (A) and the ethylene polymer component (B) is (30 to 70): (70 to 30), preferably (32 to 60): (68 to 40), more preferably (35 to 55): (65 to 45), still more preferably (40 to 50): (50 to 60).
The polymer composition may comprise other polymer components and optionally additives and/or fillers. It should be noted herein that the additive may be present in the polymer of ethylene (1) and/or mixed with the polymer of ethylene (1), for example in a mixing step for preparing the polymer composition. If the polymer composition comprises other polymer components, the amount of other polymer components typically varies between 3 and 20 wt.%, based on the total amount of ethylene polymer (1) and other polymer components.
Optional additives and fillers and their amounts are conventional in the field of film applications. Examples of such additives are, inter alia, antioxidants, process stabilizers, UV-stabilizers, pigments, fillers, antistatic additives, antiblocking agents, nucleating agents, acid scavengers and Polymer Processing Agents (PPA).
It is understood herein that any additives and/or fillers may optionally be added to a so-called masterbatch comprising the respective additive and carrier polymer. In this case, the carrier polymer is not calculated as polymer component of the polymer composition, but as the amount of the corresponding additive, based on the total amount of the polymer composition (100 wt%).
In one embodiment, the Low Density Polyethylene (LDPE) (2) may be a low density polyethylene, preferably produced in a high pressure process.
The LDPE preferably has a molecular weight of 910 to 940kg/m 3 In the range of 915 to 935kg/m, more preferably 3 Within the range of 918 to 930kg/m, still more preferably 3 Density in the range.
In addition, the melt flow rate MFR of LDPE is preferred 2 (190 ℃ C., 2.16 kg) in the range of 0.05 to 2.0g/10min, more preferably in the range of 0.10 to 1.8g/10min, still more preferably in the range of 0.10 to 1.8g/10min is in the range of 0.15 to 1.5g/10min, even more preferably.
Thus, an example of such a Low Density Polyethylene (LDPE) is the commercial product FT5230 (MFR) from Nordic chemical Co., ltd (Borealis AG) 2 :0.75g/10min; density: 923kg/m 3 )
Preferably, the polymer composition comprises at least 80.0 wt.% of the polymer (1) of ethylene and optionally and preferably additives, based on the total amount of the polymer composition (100 wt.%).
It should be noted here that the polymer of ethylene (1) may optionally comprise a prepolymer component in an amount of up to 20% by weight, which has a well known meaning in the art. In this case, the prepolymer component is calculated in one of the polymer components (A) or (B) of ethylene, preferably in the amount of the ethylene polymer component (A), based on the total amount of the ethylene polymer (1).
Thus, the multimodal polymer of ethylene (1) is preferably prepared using a coordination catalyst. More preferably, the ethylene polymer components (a) and (B) of the polymer of ethylene (1) are preferably produced using single site catalysts, including metallocene catalysts and non-metallocene catalysts, all terms having meanings well known in the art. The term "single site catalyst" refers herein to a catalytically active metallocene compound or complex in combination with a cocatalyst. The metallocene compound or complex is also referred to herein as an organometallic compound (C).
The organometallic compound (C) comprises a transition metal (M) of groups 3 to 10 of the periodic table (IUPAC 2007) or of an actinide or lanthanide.
The term "organometallic compound (C)" according to the invention includes any metallocene or non-metallocene compound of transition metal which carries at least one organic (coordinating) ligand and which exhibits catalytic activity alone or together with a cocatalyst. Transition metal compounds are well known in the art and the present invention encompasses compounds of metals of groups 3 to 10, such as groups 3 to 7, or groups 3 to 6, such as groups 4 to 6, of the periodic table (IUPAC 2007), and lanthanides or actinides.
In one embodiment, the organometallic compound (C) has the following formula (I):
(L) m R n MX q (I)
wherein the method comprises the steps of
"M" is a transition metal (M) of transition metals (M) of groups 3 to 10 of the periodic Table of the elements (IUPAC 2007),
each "X" is independently a monoanionic ligand, e.g., a sigma ligand,
each "L" is independently an organic ligand coordinated to the transition metal "M",
"R" is a bridging group linking the organic ligands (L),
"m" is 1, 2 or 3, preferably 2
"n" is 0, 1 or 2, preferably 1,
"q" is 1, 2 or 3, preferably 2, and
m+q is equal to the valence of the transition metal (M).
"M" is preferably selected from zirconium (Zr), hafnium (Hf) or titanium (Ti), more preferably from zirconium (Zr) and hafnium (Hf). "X" is preferably halogen, most preferably Cl.
Most preferably, the organometallic compound (C) is a metallocene complex comprising a transition metal compound as defined above, which comprises a cyclopentadienyl, indenyl or fluorenyl ligand as substituent "L". In addition, the ligand "L" may have a substituent such as an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, a silyl group, a siloxy group, an alkoxy group, or other hetero atom group, or the like. Suitable metallocene catalysts are known in the art and are disclosed in, inter aliA, WO-A-95/12622, WO-A-96/32423, WO-A-97/28170, WO-A-98/32776, WO-A-99/61489, WO-A-03/010208, WO-A-03/051934, WO-A-03/051514, WO-A-2004/085499, EP-A-1752462 and EP-A-1739103.
The most preferred single site catalysts are metallocene catalysts, which means catalytically active metallocene complexes as defined above in conjunction with a cocatalyst also known as an activator. Suitable activators are metal alkyl compounds, especially aluminum alkyl compounds known in the art. Particularly suitable activators for use with metallocene catalysts are alkylaluminum oxides, such as Methylaluminoxane (MAO), tetraisobutylaluminoxane (TIBAO) or Hexaisobutylaluminoxane (HIBAO).
More preferably, the ethylene polymer components (a) and (B) of the ethylene polymer (1) are produced using the same metallocene catalyst, i.e. in the presence thereof.
Preferably, the Mw/Mn of the polymer (1) of ethylene is between 2.5 and 4.8, preferably between 3.0 and < 4.5, further preferably between 3.5 and 4.2.
The multimodal polymer of ethylene (1) may be produced in any suitable polymerisation process known in the art. The ethylene polymer component (a) is preferably produced in a first polymerization zone and the ethylene polymer component (B) is produced in a second polymerization zone. The first polymerization zone and the second polymerization zone may be connected in any order, i.e. the first polymerization zone may precede the second polymerization zone, or the second polymerization zone may precede the first polymerization zone, or the polymerization zones may be connected in parallel. However, it is preferred to operate the polymerization zone in a cascade mode. The polymerization zone may be operated in slurry, solution or gas phase conditions or in a combination thereof. Suitable processes including cascaded slurry and gas phase polymerization stages are disclosed, for example, in WO-A-92/12182 and WO-A-96/18662.
It is generally preferred to remove the reactants of the preceding polymerization stage from the polymer before introducing the polymer into the subsequent polymerization stage. This is preferably done when the polymer is transferred from one polymerization stage to another.
The catalyst may be transferred to the polymerization zone by any means known in the art. For example, the catalyst may be suspended in a diluent and maintained as a homogeneous slurry, the catalyst mixed with a viscous mixture of grease and oil and the resulting slurry fed to the polymerization zone or the catalyst allowed to settle and a portion of the catalyst mud thus obtained introduced into the polymerization zone.
The polymerization in the first polymerization zone, preferably the polymerization of the ethylene polymer component (a), is preferably carried out in a slurry. The polymer particles formed in the polymerization are then suspended in the fluid hydrocarbon along with the catalyst broken up and dispersed in the particles. The slurry is stirred to transfer the reactants from the fluid into the particles.
The polymerization is typically carried out in an inert diluent, typically a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentane, hexane, heptane, octane, and the like, or mixtures thereof. Preferably, the diluent is a low boiling hydrocarbon having 1 to 4 carbon atoms or a mixture of such hydrocarbons, the preferred diluent being propane.
The ethylene content in the fluid phase of the slurry may be from 2 to about 50 mole%, preferably from about 2 to about 20 mole%, and especially from about 3 to about 12 mole%.
The temperature in slurry polymerization is generally 50 to 115 ℃, preferably 60 to 110 ℃, especially 70 to 100 ℃. The pressure is from 1 to 150 bar, preferably from 10 to 100 bar.
The slurry polymerization may be carried out in any known reactor for slurry polymerization. Such reactors include continuous stirred tank reactors and loop reactors. The polymerization is particularly preferably carried out in a loop reactor. In such a reactor, the slurry is circulated at a high speed along a closed pipe by using a circulation pump. Loop reactors are generally known in the art and examples are given, for example, in US-se:Sup>A-4582816, US-se:Sup>A-3405109, US-se:Sup>A-3324093, EP-se:Sup>A-479186 and US-se:Sup>A-5391654.
It is sometimes advantageous to carry out the slurry polymerization above the critical temperature and pressure of the fluid mixture. Such an operation is described in US-se:Sup>A-5391654. In such an operation, the temperature is generally from 85 to 110 ℃, preferably from 90 to 105 ℃, and the pressure is from 40 to 150 bar, preferably from 50 to 100 bar.
The slurry may be withdrawn from the reactor continuously or intermittently. The preferred way of intermittent withdrawal is to use settling legs (settling legs) where the slurry is allowed to concentrate before a batch of concentrated slurry is withdrawn from the reactor. The continuous withdrawal is advantageously combined with suitable concentration methods, as disclosed for example in EP-A-1310295 and EP-A-1591460.
Hydrogen may be fed into the reactor to control the molecular weight of the polymer, as is known in the art. In addition, one or more alpha olefin comonomers are added to the reactor, for example to control the density of the polymer product. The actual amounts of such hydrogen and comonomer feeds will depend on the catalyst used and the desired melt index (or molecular weight) and density (or comonomer content) of the resulting polymer.
The polymerization in the second polymerization zone, preferably the polymerization of the ethylene polymer component (B), is preferably carried out in the gas phase, preferably in a fluidized bed reactor, in a fast fluidized bed reactor or in a settled bed reactor or in any combination of these. The polymerization in the second polymerization zone is more preferably carried out in a fluidized bed gas phase reactor, wherein ethylene is polymerized with at least one comonomer in the presence of a polymerization catalyst, and preferably in an upwardly moving gas stream in the presence of the reaction mixture comprising the ethylene polymer component (a) from the first polymerization zone. The reactor typically contains a fluidized bed containing growing polymer particles containing active catalyst located above a fluidization grid.
The polymer bed is fluidized with the aid of a fluidizing gas comprising olefin monomer, final comonomer, final chain growth control agent or chain transfer agent, e.g. hydrogen, and final inert gas. The fluidizing gas is introduced into the inlet chamber at the bottom of the reactor. One or more of the above components may be added continuously to the fluidizing gas to compensate for losses due to, for example, reaction or product removal, etc.
The fluidizing gas passes through the fluidized bed. The superficial velocity of the fluidization gas must be higher than the minimum fluidization velocity of the particles contained in the fluidized bed, otherwise fluidization does not occur. On the other hand, the velocity of the gas should be lower than the initial velocity of the pneumatic transport, otherwise the entire bed will be entrained with the fluidizing gas.
When the fluidizing gas is contacted with a bed containing an active catalyst, the reactive components of the gas, such as the monomer and chain transfer agent, react in the presence of the catalyst to form a polymer product. At the same time, the gas is heated by the heat of reaction.
Unreacted fluidizing gas is withdrawn from the top of the reactor and cooled in a heat exchanger to remove the heat of reaction. The gas is cooled to a temperature below the bed to prevent the bed from heating up due to the reaction. The gas may be cooled to a temperature at which a portion thereof condenses. As the droplets enter the reaction zone they are vaporized. The heat of vaporization then helps to remove the heat of reaction. This type of operation is called condensing mode and its variants are disclosed, for example, in WO-A-2007/025640, US-A-4543399, EP-A-699213 and WO-A-94/25495. Condensing agents may also be added to the recycle gas stream as disclosed in EP-A-696293. The condensing agent is a non-polymerizable component that is at least partially condensed in the cooler, such as n-pentane, isopentane, n-butane, or isobutane.
The gas is then compressed and recycled to the inlet chamber of the reactor. Fresh reactants are introduced into the fluidization gas stream prior to entering the reactor to compensate for losses caused by reaction and product withdrawal. It is generally known to analyze the composition of the fluidizing gas and introduce the gas composition to keep the composition constant. The actual composition depends on the desired product properties and the catalyst used in the polymerization.
The catalyst may be introduced into the reactor in various ways, either continuously or intermittently. When the gas phase reactor is part of a reactor cascade, the catalyst is typically dispersed in the polymer particles from the previous polymerization stage. The polymer particles may be introduced into A gas phase reactor as disclosed in EP-A-1415999 and WO-A-00/26158. In particular, as disclosed in EP-A-887379, EP-A-887380, EP-A-887381 and EP-A-991684, it is advantageous if the preceding reactor is a slurry reactor, to feed the slurry directly into the fluidized bed of the gas phase reactor.
The polymerization product may be withdrawn from the gas phase reactor continuously or intermittently. Combinations of these methods may also be used. Continuous removal is disclosed in WO-A-00/29452 et al. Intermittent removal is disclosed in US-A-4621952, EP-A-188125, EP-A-250169 and EP-A-579426, etc.
Antistatic agents such as water, ketones, aldehydes, alcohols, and the like may also be introduced into the gas phase reactor if desired. The reactor may also include a mechanical agitator to further promote mixing within the fluidized bed.
Typically the fluidised bed polymerisation reactor is operated at a temperature in the range 50 to 100 ℃, preferably 65 to 90 ℃. The pressure is suitably from 10 to 40 bar, preferably from 15 to 30 bar.
The polymerization of at least the ethylene polymer component (a) and the ethylene polymer component (B) in the first and second polymerization zones may be carried out prior to the prepolymerization step. The purpose of the prepolymerization is to polymerize small amounts of polymer onto the catalyst at low temperatures and/or low monomer concentrations. By pre-polymerization, the performance of the catalyst in the slurry can be improved and/or the final polymer properties can be altered. The prepolymerization step can be carried out in slurry or gas phase. Preferably, the prepolymerization is carried out in a slurry, preferably in a loop reactor. The prepolymerization is then preferably carried out in an inert diluent, preferably a low boiling hydrocarbon having 1 to 4 carbon atoms or a mixture of these hydrocarbons.
The temperature in the prepolymerization step is usually 0 to 90 ℃, preferably 20 to 80 ℃, more preferably 40 to 70 ℃.
The pressure is not critical and is generally from 1 to 150 bar, preferably from 10 to 100 bar.
The catalyst components are preferably all introduced into the prepolymerization step. Preferably, the reaction product of the prepolymerization step is then introduced into the first polymerization zone. Also preferably, as described above, the prepolymer component is calculated as the amount of the ethylene polymer component (a).
The polymerization conditions as well as the feed stream and residence time are adjusted in each step to obtain the multimodal polymer of ethylene (1) as claimed, which is within the knowledge of the skilled person.
Multimodal polymer (1) comprising at least ethylene, preferably comprising only ethylene polymer components (a) and (B) obtained from a second polymerization zone, preferably a gas phase reactor as described above, is subjected to conventional post reactor treatment to remove e.g. unreacted components.
Thereafter, the polymer obtained is generally extruded and pelletized. Extrusion may be carried out in a manner generally known in the art, preferably in a twin screw extruder. One example of a suitable twin screw extruder is a co-rotating twin screw extruder. These are manufactured, for example, by Coperion (Coperion) or Japanese Steel institute (Japan Steel Works). Another example is a counter-rotating twin screw extruder. Such extruders are mainly manufactured by, for example, kobe Steel and Japanese Steel. At least part of the desired additives are preferably mixed with the polymer prior to extrusion, as described above. The extruder typically includes a melting section that melts the polymer and a mixing section that homogenizes the polymer melt. Melting and homogenization is achieved by introducing energy into the polymer. Suitable levels of Specific Energy Input (SEI) are from about 150 to about 450 kWh/ton of polymer, preferably from 175 to 350 kWh/ton.
The film of the invention
The film of the present invention comprises at least one layer comprising said polymer composition.
The film may be a single layer film comprising the polymer composition or a multilayer film wherein at least one layer comprises the polymer composition. The terms "monolayer film" and "multilayer film" have well known meanings in the art.
The layers of the monolayer or multilayer film of the present invention may consist of the polymer composition itself or of a blend of the polymer composition with other polymers. In the case of the blend, any other polymer is different from the polymer (1) of ethylene and is preferably a polyolefin. Some of the above additives, such as processing aids, may optionally be added to the polymer composition during film preparation.
Preferably, at least one layer of the present invention comprises at least 50 wt%, preferably at least 60 wt%, preferably at least 70 wt%, more preferably at least 80 wt% of the polymer composition of the present invention. More preferably, at least one layer of the film of the present invention consists of said polymer composition.
Thus, the films of the present invention may comprise a single layer (i.e., a monolayer) or may be multi-layered. The multilayer film generally and preferably comprises at least 3 layers.
The film is preferably produced by any conventional film extrusion procedure known in the art, including cast film and blown film extrusion. Most preferably, the film is a blown or cast film. For example, blown films are produced by extrusion through an annular die and blown into a tubular film by forming bubbles that collapse between nip rolls after curing. The film may then be slit, cut or converted (e.g., gusseted) as desired. Conventional film production techniques may be used in this regard. If the preferred blown or cast film is a multilayer film, the layers are typically coextruded. The skilled person will know suitable extrusion conditions.
The resulting film may have any thickness conventional in the art. The thickness of the film is not critical and depends on the end use. Thus, the film may have a thickness of, for example, 300 μm or less, typically 6 to 200 μm, preferably 10 to 180 μm, for example 20 to 150 μm or 20 to 120 μm. The polymers of the invention can achieve a thickness of less than 100 μm, for example less than 50 μm, if desired. It is also possible to produce films of the invention having a thickness of even less than 20 μm while maintaining good mechanical properties.
Measurement method
Unless otherwise indicated in the description or in the experimental section, the following methods are used for the determination of properties of the polymer composition and/or any sample preparation thereof as specified in the text or experimental section.
Melt flow Rate
Melt Flow Rate (MFR) is determined according to ISO 1133 and is expressed in g/10 min. MFR is an indicator of polymer flowability and thus processability. The higher the melt flow rate, the lower the viscosity of the polymer. For polyethylene, MFR was determined at 190 ℃. The MFR can be determined under different loads, e.g. 2.16kg (MFR 2 )、5kg(MFR 5 ) Or 21.6kg (MFR) 21 )。
Density of
On compression molded test specimens prepared according to EN ISO 1872-2 (month 2 2007), according to ASTM; d792, method B (equilibrium Density at 23 ℃ C.) measuring the Density of the Polymer in kg/m 3 。
Molecular weight, molecular weight distribution (Mn, mw, MWD) -GPC
PL 220 (Agilent) GPC was used, equipped with Refractive Index (RI), an in-line four-capillary bridge viscometer (PL-BV 400-HT), and a double light scattering detector (PL-LS 15/90 light scattering detector) with angles of 15℃and 90 ℃. Agilent 3x oxides and 1x oxides Guard chromatography columns were used as stationary phases and 1,2, 4-trichlorobenzene (TCB stabilized with 250 mg/L2, 6-di-tert-butyl-4-methylphenol) as mobile phase at 160℃and constant flow rate of 1 mL/min. 200uL of sample solution was injected per analysis . All samples were prepared by dissolving 8.0-12.0mg of polymer in 10mL (160 ℃) of stabilized TCB (same as mobile phase) at 160℃for 2.5 hours (for PP) or 3 hours (for PE) with continuous gentle shaking. Injection concentration of polymer solution at 160 ℃ (c 160℃ ) Determined as follows.
Wherein: w (W) 25 (Polymer weight) and V 25 (volume of TCB at 25 ℃).
The narrow PS standard (mwd=1.01), a molar mass of 132900g/mol and a viscosity of 0.4789dl/g were used to determine the corresponding detector constants and inter-detector delay volumes. The PS standard used in TCB corresponds to a dn/dc of 0.053cm 3 And/g. Calculations were performed using Cirrus Multi-Offline SEC software version 3.2 (Agilent).
The molar mass of each elution slice was calculated by using a 15 ° light scattering angle. Cirrus MultiSEC software version 3.2 was subjected to data collection, data processing and calculation. Molecular weight was calculated using LS 15angle in the "sample calculation options subfield slice MW data from (sample calculation options subfield slice MW data from)" field using the options in Cirrus software. The dn/dc used to determine the molecular weight is calculated from the detector constant of the RI detector, the concentration c of the sample, and the detector response area of the analyzed sample.
This molecular weight for each slice was calculated at low angles as described by c.jackson and h.g. barth (c.jackson and h.g. barth, "Molecular Weight Sensitive Detectors" in the Size Exclusion Chromatography and related technologies handbook, c. -s.wu, 2 nd edition, marcel Dekker, new york, 2004, page 103). For low and high molecular regions where less signal is obtained for the LS detector or RI detector, respectively, a linear fit is used to relate the elution volumes to the corresponding molecular weights. The area of the linear fit was adjusted according to the sample.
Molecular weight averages (Mz, mw, and Mn), molecular Weight Distribution (MWD), and widths thereof (which are described by polydispersity index, pdi=mw/Mn (where Mn is the number average molecular weight, mw is the weight average molecular weight)) are determined by Gel Permeation Chromatography (GPC) according to ISO 16014-4:2003 and ASTM D6474-99 using the following formulas:
for a constant elution volume interval DeltaV i Wherein A is i And M i Is the chromatographic peak slice area and polyolefin Molecular Weight (MW) determined by GPC-LS.
Comonomer content:
quantification of microstructure by NMR Spectroscopy
Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer.
For a Bruker Advance III 500NMR spectrometer 1 H and 13 c was run at 500.13 and 125.76MHz respectively, and the quantification was recorded in the molten state 13 C {1H } NMR spectrum. For all pneumatic techniques nitrogen is used, using 13 C optimized 7mm magic angle turning (MAS) probe all spectra were recorded at 150 ℃. Approximately 200mg of material was charged into a zirconia MAS rotor having an outer diameter of 7mm and rotated at a frequency of 4 kHz. This setting is chosen mainly because of the high sensitivity required for fast identification and accurate quantification. Standard single pulse excitation of { klimke06, parkinson07, castignoles 09} was performed using a short loop delay NOE { polard 04, klimke06} and an RS-HEPT decoupling scheme { filep 05, griffin07 }. A total of 1024 (1 k) transients were obtained for each spectrum.
To quantitative determination 13 C{ 1 H } NMR spectra are processed, integrated, and the quantitative nature of the correlation is determined from the integration. All chemical shifts are referenced internally to the bulk methylene signal (δ+) at 30.00 ppm.
The ethylene amount was quantified using the integration of the methylene (δ+) sites at 30.00ppm, accounting for the reported number of sites per monomer:
E＝I δ+ /2
correcting the presence of the isolated comonomer units based on the number of isolated comonomer units present:
E total (S) ＝E+(3*B+2*H)/2
Wherein B and H are defined for their respective comonomers. Correction for continuous and discontinuous comonomer incorporation (if present) is performed in a similar manner.
Observing a characteristic signal corresponding to 1-butene incorporation, the comonomer fraction is calculated as the fraction of 1-butene in the polymer relative to all monomers in the polymer:
fB total (S) ＝(B Total (S) /(E Total (S) +B Total (S) +H Total (S) )
Use at 38.3ppm * Integration of the B2 site to quantify the amount of isolated 1-butene incorporated in the EEBEEs sequence, indicates the number of reported sites per comonomer:
B＝I *B2
the amount of continuously incorporated 1-butene in the EEBBEE sequence was quantified using integration at the ααb2b2 site at 39.4ppm, accounting for the number of reported sites per comonomer:
BB＝2*IααB2B2
the amount of discontinuously incorporated 1-butene in the eebee sequence was quantified using integration at the ββb2b2 site at 24.7ppm, accounting for the number of reported sites per comonomer:
BEB＝2*IββB2B2
since the isolated (EEBEE) and discontinuously incorporated (EEBEE) 1-butene have respective overlapping B2 and βb2b2 sites, the total amount of isolated 1-butene incorporation is corrected based on the amount of discontinuous 1-butene present:
B＝I *B2 -2*I ββB2B2
the total 1-butene content was calculated based on the sum of the isolated, continuous and discontinuously incorporated 1-butenes:
B total (S) ＝B+BB+BEB
The total mole fraction of 1-butene in the polymer was then calculated as:
fB＝(B total (S) /(E Total (S) +B Total (S) +H Total (S) )
Observing the characteristic signal corresponding to 1-hexene incorporation, the comonomer fraction was calculated as the fraction of 1-hexene in the polymer relative to all monomers in the polymer:
fH Total (S) ＝(H Total (S) /(E Total (S) +B Total (S) +H Total (S) )
Use at 39.9ppm * Integration of the B4 site to quantify the amount of isolated 1-hexene incorporated in the EEHEE sequence, indicates the number of reported sites per comonomer:
H＝I *B4
the amount of continuously incorporated 1-hexene in the EEHHEE sequence was quantified using integration at the ααb4b4 site at 40.5ppm, accounting for the reported number of sites per comonomer:
HH＝2*IααB4B4
the amount of discontinuously incorporated 1-hexene in the eehehe sequence was quantified using integration at the ββb4b4b4site at 24.7ppm, indicating the number of reported sites per comonomer:
HEH＝2*IββB4B4
the total mole fraction of 1-hexene in the polymer was then calculated as:
fH＝(H total (S) /(E Total (S) +B Total (S) +H Total (S) )
The mole percent of comonomer incorporation is calculated from the mole fraction:
b [ mol% ] =100×fb
H [ mol% ] = 100 x fh
The weight percent of comonomer incorporation is calculated from the mole fraction:
b [ wt% ] =100 (fB 56.11)/((fB 56.11) + (fH 84.16) + (1- (fb+fh)). 28.05)
H [ wt% ] =100× (fh×84.16)/((fb×56.11) + (fh×84.16) + (1- (fb+fh))× 28.05)
Reference is made to:
klimke06:Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.
parkinson07:Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.
pollard04:Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.
filip05:Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239
griffin07:Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.in Chem.2007 45,S1,S198
castignolles09:Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373
busico01:Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443
busico97:Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L.,Macromoleucles30(1997)6251
zhou07:Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225
busico07:Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128
resconi00:Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253
sealing performance:
seal Initiation Temperature (SIT); sealing End Temperature (SET), sealing range:
the method determines the sealing temperature range (sealing range) of polypropylene films, in particular blown films or cast films. The sealing temperature range is a temperature range in which the film can be sealed according to the conditions given below.
The lower limit (heat Seal Initiation Temperature (SIT)) is the sealing temperature at which a seal strength of >5N is reached. When the film sticks to the sealing device, the upper limit (seal end temperature (SET)) is reached.
The sealing range was determined by a J & B4000 type universal sealer with a film thickness of 40. Mu.m
With the following further parameters:
sample width: 25.4mm
Sealing pressure: 0.1N/mm 2
Sealing time: 0.1 second
Cooling time: 99 seconds
Peeling speed: 10 mm/sec
Starting temperature: 80 DEG C
End temperature: 150 DEG C
Increment: 5 DEG C
Samples were sealed from a to a at each seal bar temperature and seal strength (force) was determined at each step.
The temperature at which the seal strength reached 5N was determined.
Haze:
haze was measured according to ASTM D1003-00 on films produced as shown below.
Gloss level:
gloss was measured according to ASTM D2457 at a 45 ° angle (in MD) on films produced as shown below. Adjusting time: 96 h/test temperature: 23 DEG C
Experimental part
Preparation of the examples
Catalyst examples: catalyst preparation
130 g of the metallocene complex bis (1-methyl-3-n-butylcyclopentadienyl) zirconium (IV) dichloride (CAS No. 151840-68-5) and 9.67kg of a 30% commercial Methylaluminoxane (MAO) in toluene were combined and 3.18kg of dry purified toluene was added. The complex solution thus obtained was applied by spraying very slowly and uniformly over 2 hours onto 17kg of the silica support Sylopol 55SJ (supplied by Grace). The temperature was kept below 30 ℃. After addition of the complex, the mixture was allowed to react at 30℃for 3 hours.
Polymerization: inventive example 1: multimodal polymers of inventive ethylene with 1-butene and 1-hexene comonomers
A Borstar pilot plant with 3 reactor units (loop 1-loop 2-GPR 1) and a prepolymerized loop reactor.
Prepolymerization: volume of 50dm 3 The loop reactor was operated at a temperature of 50℃and a pressure of 5.7 MPa.
Furthermore, the volume was 150dm 3 Is operated at a temperature of 85 ℃ and at 5.5 MPa. Volume of 350dm 3 The second loop reactor of (2) was operated at 85℃and 5.4 MPa.
From there, the polymer was led to a flash vessel operated at 300kPa, then to a Gas Phase Reactor (GPR) operated at a pressure of 2.2MPa and a temperature of 75 ℃.
The polymerization conditions and material properties are listed in the following table.
The polymer composition of the invention:
the polymer composition of the invention was prepared from 90.0% by weight of inventive example (IE 1) and 10.0% by weight of a commercial linear low density polyethylene (vendor Borealis, MFR) sold under the trade name FT5230 in a high pressure process 2 :0.75g/10min; density: 923kg/m 3 ) Composition is prepared. The% by weight is based on the total amount of the two polymer components.
Membrane sample preparation
Test films of 40 μm thickness composed of the polymer composition of the invention (final polymer composition), the blend composition of the invention and the corresponding comparative or reference polymer composition were prepared using a Collin 30 laboratory-scale monolayer blown film line.
The screw diameter of the production line is 25 millimeters (mm), the L/D is 25, the diameter of the die is 60mm, and the die gap is 1.5mm. Film samples were produced at 190℃with an average thickness of 40 μm, a blow-up ratio of 1:3 and a frost line distance of 120mm. The melt temperature was 194 ℃.
In the case of producing film samples of the blend compositions of the present invention, the two polymer components are dry blended and then fed to an extruder.
Table 1: polymerization conditions of multimodal Polymer of ethylene (1) Comparison (CE) and Invention (IE)
The polymer was mixed with 2400ppm Irganox B561, kneaded and extruded into pellets using a CIMP90 extruder under nitrogen atmosphere to make SEI 230kWh/kg and melt temperature 250 ℃.
Table 2: material Properties
Material CE IE
MFR2(g/10min) 1.7 2.8
MFR21.6(g/10min) 35.7 57.5
MFR21/MFR2 20.9 20.7
Mn 21750 20550
Mw 91400 81350
Mz 178500 155000
Mw/Mn 4.2 4.0
Density (kg/m 3) 918 913.1
C4 (mol%) 0.2 0.2
C6 (mol%) 2.8 3.6
Table 3: film Properties without LDPE (comparative examples CE1 and CE 2) (films made of CE and IE materials, without LDPE addition)
CE1 CE2
LDPE (2) (wt.%) 0 0
PE (1) (wt.%) 100％CE 100％IE
SIT 83 68
Gloss (MD) 45 DEG C 17.9 16.1
Haze degree 35 42.2
Table 4: film Properties Using LDPE (film made of CE and IE materials and LDPE added)
CE3 IE1
LDPE (2) (wt.%) 10 10
PE (1) (wt.%) 90％CE 90％IE
SIT 91 68
Gloss (MD) 45 DEG C 70.2 67.8
Haze degree 7.1 10.4
Inventive example IE1 thus shows improved optical properties, such as improved gloss and haze relative to CE1 and CE2, and unexpectedly improved/reduced SIT relative to CE3 and CE 1. In particular, comparison of CE2 and IE1 shows that SIT is unexpectedly unaffected by the addition of LDPE, whereas comparison of CE1 and CE3 shows that in that case, the addition of LDPE makes SIT worse/increased.

Claims (43)

1. A polymer composition comprising
80.0-99.0 wt%, based on the total weight of the polymer composition, (1) a multimodal polymer of ethylene with at least two different comonomers selected from alpha olefins having 4 to 10 carbon atoms,
the multimodal polymer of ethylene has the following properties
a) MFR measured at 190℃and under a load of 2.16kg according to ISO 1133 2 0.5 to 10g/10min,
b)MFR 21 /MFR 2 13 to 35, where MFR 21 Measured at 190℃under a load of 21.6kg, and
c) Mw/Mn is 5 or less; and
the multimodal polymer of ethylene comprises at least
Ethylene Polymer Components (A) and
an ethylene polymer component (B),
MFR of the ethylene polymer component (a) 2 Different fromMFR of the ethylene polymer component (B) 2 And (b)
The multimodal polymer of ethylene (1) is further multimodal in terms of density, the density of the ethylene polymer component (A) being higher than the density of the ethylene polymer component (B)>41kg/m 3 ，
And 1.0 to 20.0 weight percent of (2) LDPE based on the total weight of the polymer composition.
2. The polymer composition according to claim 1, wherein the ethylene polymer component (a) has an MFR 2 1 to 50g/10min and/or wherein the amount of (1) is between 85.0 and 99.0 wt% based on the total weight of the polymer composition, and the amount of (2) is between 1.0 and 15.0 wt% based on the total weight of the polymer composition.
3. The polymer composition according to claim 2, wherein the ethylene polymer component (a) has MFR 2 1 to 40g/10min.
4. The polymer composition according to claim 2, wherein the ethylene polymer component (a) has MFR 2 1 to 30g/10min.
5. The polymer composition of claim 2, wherein the amount of (1) is between > 85.0 and 95.0 wt%, based on the total weight of the polymer composition.
6. The polymer composition of claim 2, wherein the amount of (2) is between 5.0 and <15.0 wt% based on the total weight of the polymer composition.
7. The polymer composition according to any one of claims 1 to 6, wherein the ethylene polymer component (a) has MFR 2 MFR higher than the ethylene polymer component (B) 2 。
8. The polymer composition of claim 7, wherein the ethylene polymerMFR of component (A) 2 MFR of multimodal polymer (a) with final ethylene 2 The ratio is 1 to 50.
9. The polymer composition according to claim 7, wherein the ethylene polymer component (A) has MFR 2 MFR of multimodal polymer (a) with final ethylene 2 The ratio is 1.5 to 40.
10. The polymer composition according to claim 7, wherein the ethylene polymer component (A) has MFR 2 MFR of multimodal polymer (a) with final ethylene 2 The ratio is 1.8 to 30.
11. The polymer composition according to claim 7, wherein the ethylene polymer component (A) has MFR 2 MFR of multimodal polymer (a) with final ethylene 2 The ratio is 2.0 to 25.
12. The polymer composition of any of claims 1-6, wherein at least two alpha olefin comonomers having 4 to 10 carbon atoms are 1-butene and 1-hexene.
13. The polymer composition according to any of claims 1-6, wherein the multimodal polymer of ethylene (1) is further multimodal in terms of comonomer type and/or comonomer content.
14. The polymer composition of claim 13, wherein the alpha olefin comonomer having 4 to 10 carbon atoms of ethylene polymer component (a) is different from the alpha olefin comonomer having 4 to 10 carbon atoms of ethylene polymer component (B).
15. The polymer composition of claim 13, wherein the alpha olefin comonomer of 4 to 10 carbon atoms of ethylene polymer component (a) is 1-butene and the alpha olefin comonomer of 4 to 10 carbon atoms of ethylene polymer component (B) is 1-hexene.
16. The polymer composition according to any of claims 1-6, wherein the ratio of [ the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a), in mole%, to [ the amount of at least two alpha olefin comonomers having 4 to 10 carbon atoms of the final multimodal polymer of ethylene (1), in mole%, is 0.1 to 0.6.
17. The polymer composition according to claim 16, wherein the ratio of [ the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a), in mol-% ] to [ the amount of at least two alpha olefin comonomers having 4 to 10 carbon atoms of the final multimodal polymer of ethylene (1), in mol-% ] is 0.1 to 0.4.
18. The polymer composition of claim 16, wherein the amount of comonomer of ethylene polymer component (a) in mole percent is lower than the amount of comonomer of ethylene polymer component (B) in mole percent.
19. The polymer composition of any of claims 1-6, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) is 0.03 to 5.0 mole percent and/or the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (B) is 0.3 to 10.0 mole percent.
20. The polymer composition of claim 19, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) is 0.05 to 4.0 mole percent.
21. The polymer composition of claim 19, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) is 0.1 to 3.0 mole percent.
22. The polymer composition of claim 19, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (a) is 0.1 to 2.0 mole percent.
23. The polymer composition of claim 19, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (B) is 0.5 to 9.0 mole percent.
24. The polymer composition of claim 19, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (B) is 1.0 to 8.5 mole percent.
25. The polymer composition of claim 19, wherein the amount of alpha olefin comonomer having 4 to 10 carbon atoms present in the ethylene polymer component (B) is 3.0 to 8.0 mole percent.
26. The polymer composition according to any of claims 1-6, wherein the multimodal polymer of ethylene (1) is further multimodal in terms of density, the density of the ethylene polymer component (a) being > 42 or 42.5kg/m higher than the density of the ethylene polymer component (B) 3 。
27. The polymer composition according to any one of claims 1-6, wherein the ethylene polymer component (a) has a density of 925 to 950kg/m 3 And/or the ethylene polymer component (B) has a density of 880 to<910kg/m 3 。
28. The polymer composition of claim 27, wherein the ethylene polymer component (a) has a density of 930 to 945kg/m 3 。
29. The polymer combination of claim 27The ethylene polymer component (B) having a density of 890 to 905kg/m 3 。
30. The polymer composition according to any of claims 1-6, wherein the multimodal polymer of ethylene (1) has a density of 910 to 935kg/m 3 。
31. The polymer composition according to claim 30, wherein the multimodal polymer of ethylene (1) has a density of 912 to 925kg/m 3 。
32. The polymer composition according to any of claims 1-6, wherein the multimodal polymer of ethylene (1) has an MFR of from 13 to 30 21 /MFR 2 。
33. The polymer composition according to claim 32, wherein the multimodal polymer of ethylene (1) has an MFR of from 15 to 30 21 /MFR 2 。
34. The polymer composition according to any of claims 1-6, wherein the multimodal polymer of ethylene (1) is multimodal in terms of MFR, type of comonomer, comonomer content and density.
35. The polymer composition according to any of claims 1-6, wherein the polymer compositions of (1) and (2) have a Seal Initiation Temperature (SIT) as determined in the experimental section, which is equal to or within plus or minus 2.5 ℃ of the SIT of (1), and/or wherein the SIT of the polymer compositions of (1) and (2) is between 55 ℃ and 90 ℃.
36. The polymer composition of claim 35, wherein the SIT of the polymer compositions of (1) and (2) is between 60 ℃ and 80 ℃.
37. The polymer composition of claim 35, wherein the SIT of the polymer compositions of (1) and (2) is between 62 ℃ and 75 ℃.
38. The polymer composition of claim 35, wherein the SIT of the polymer compositions of (1) and (2) is in the range of >62 ℃ and 70 ℃.
39. The polymer composition according to any of claims 1-6, wherein the multimodal polymer of ethylene (1) is produced using a single site catalyst and/or wherein the Mw/Mn of the multimodal polymer of ethylene (1) is between 2.5 and 4.8.
40. The polymer composition of claim 39, wherein the ethylene polymer components (A) and (B) of the ethylene polymer (1) are produced using the same single site catalyst.
41. The polymer composition according to claim 39 wherein the multimodal polymer of ethylene (1) has a Mw/Mn of between 3.0 and < 4.5.
42. The polymer composition according to claim 39 wherein the multimodal polymer of ethylene (1) has a Mw/Mn of between 3.5 and 4.2.
43. An article comprising the polymer composition of any one of claims 1 to 42, or a film comprising at least one layer comprising the polymer composition of any one of the preceding claims 1 to 42.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107001663A (en) * 2014-11-26 2017-08-01 博里利斯股份公司 Polyethylene composition for film layer

Family Cites Families (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3405109A (en) 1960-10-03 1968-10-08 Phillips Petroleum Co Polymerization process
US3324093A (en) 1963-10-21 1967-06-06 Phillips Petroleum Co Loop reactor
US4621952A (en) 1981-07-28 1986-11-11 Union Carbide Corporation Fluidized bed discharge process
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
AU576409B2 (en) 1984-12-31 1988-08-25 Mobil Oil Corporation Fluidized bed olefin polymerization process
US4582816A (en) 1985-02-21 1986-04-15 Phillips Petroleum Company Catalysts, method of preparation and polymerization processes therewith
FR2599991B1 (en) 1986-06-16 1993-04-02 Bp Chimie Sa EVACUATION OF PRODUCTS PRESENT IN AN ALPHA-OLEFIN POLYMERIZATION REACTOR IN A FLUIDIZED BED
US5565175A (en) 1990-10-01 1996-10-15 Phillips Petroleum Company Apparatus and method for producing ethylene polymer
FI89929C (en) 1990-12-28 1993-12-10 Neste Oy Process for homo- or copolymerization of ethylene
FI86867C (en) 1990-12-28 1992-10-26 Neste Oy FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN
EP0579426B1 (en) 1992-07-16 1998-03-18 BP Chemicals Limited Polymerization process
ES2148327T5 (en) 1993-04-26 2009-11-17 Univation Technologies, Llc PROCEDURE TO POLYMERIZE MONOMEROS IN FLUIDIZED MILKS.
CA2161419C (en) 1993-04-26 1999-05-04 Marc Louis Dechellis Process for polymerizing monomers in fluidized beds
ZA943399B (en) 1993-05-20 1995-11-17 Bp Chem Int Ltd Polymerisation process
FI96866C (en) 1993-11-05 1996-09-10 Borealis As Support olefin polymerization catalyst, its preparation and use
FI96216C (en) 1994-12-16 1996-05-27 Borealis Polymers Oy Process for the production of polyethylene
FI104975B (en) 1995-04-12 2000-05-15 Borealis As Process for producing catalytic components
FI104826B (en) 1996-01-30 2000-04-14 Borealis As Heteroatom-substituted metallose compounds for catalytic systems in olefin polymerization and process for their preparation
FI972230A (en) 1997-01-28 1998-07-29 Borealis As New homogeneous catalyst composition for polymerization of olefins
FI111845B (en) 1997-06-24 2003-09-30 Borealis Tech Oy Process for producing propylene homopolymers and polymers with modified impact strength
FI111846B (en) 1997-06-24 2003-09-30 Borealis Tech Oy Process and apparatus for preparing mixtures of polypropylene
FI111848B (en) 1997-06-24 2003-09-30 Borealis Tech Oy Process and equipment for the preparation of homopolymers and copolymers of propylene
FI111847B (en) 1997-06-24 2003-09-30 Borealis Tech Oy A process for the preparation of copolymers of propylene
FI981148A (en) 1998-05-25 1999-11-26 Borealis As New activator system for metallocene compounds
FI982388A (en) 1998-11-04 2000-05-05 Borealis Polymers Oy Procedure for the elimination of static electricity
FI111953B (en) 1998-11-12 2003-10-15 Borealis Tech Oy Process and apparatus for emptying polymerization reactors
GB0118010D0 (en) 2001-07-24 2001-09-19 Borealis Tech Oy Catalysts
ATE367198T1 (en) 2001-10-30 2007-08-15 Borealis Tech Oy POLYMERIZATION REACTOR
ES2321806T3 (en) 2001-12-19 2009-06-12 Borealis Technology Oy PRODUCTION OF SUPPORTED CATALYSTS FOR OLEFIN POLYMERIZATION.
EP1323747A1 (en) 2001-12-19 2003-07-02 Borealis Technology Oy Production of olefin polymerisation catalysts
ES2236371T5 (en) 2002-02-04 2011-08-01 Borealis Technology Oy LAMINARY MATERIAL WITH HIGH IMPACT RESISTANCE.
DE60223926T2 (en) 2002-10-30 2008-11-13 Borealis Technology Oy Process and apparatus for the production of olefin polymers
EP1462464A1 (en) 2003-03-25 2004-09-29 Borealis Technology Oy Metallocene catalysts and preparation of polyolefins therewith
EP1591460B1 (en) 2004-04-29 2006-06-14 Borealis Technology Oy Process for producing polyethylene
EP1739103A1 (en) 2005-06-30 2007-01-03 Borealis Technology Oy Catalyst
EP1752462B1 (en) 2005-08-09 2009-03-18 Borealis Technology Oy Siloxy substituted metallocene catalysts
CN1923861B (en) 2005-09-02 2012-01-18 北方技术股份有限公司 Olefin polymerization method with olefin polymerization catalyst
US10494465B2 (en) * 2014-11-26 2019-12-03 Borealis Ag Film layer
WO2019081611A1 (en) * 2017-10-24 2019-05-02 Borealis Ag Multilayer polymer film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107001663A (en) * 2014-11-26 2017-08-01 博里利斯股份公司 Polyethylene composition for film layer

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