CN114364735A - Process for preparing polymer compositions - Google Patents
Process for preparing polymer compositions Download PDFInfo
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- CN114364735A CN114364735A CN202080062123.1A CN202080062123A CN114364735A CN 114364735 A CN114364735 A CN 114364735A CN 202080062123 A CN202080062123 A CN 202080062123A CN 114364735 A CN114364735 A CN 114364735A
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- ethylene polymer
- ethylene
- polymer component
- polymerization
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- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 229920000573 polyethylene Polymers 0.000 claims abstract description 118
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005977 Ethylene Substances 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 239000004711 α-olefin Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000000499 gel Substances 0.000 claims description 30
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 20
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical compound [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 101100023124 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfr2 gene Proteins 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 230000003287 optical effect Effects 0.000 description 27
- 239000000463 material Substances 0.000 description 11
- 230000007547 defect Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- CKNXPIUXGGVRME-UHFFFAOYSA-L CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 Chemical compound CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 CKNXPIUXGGVRME-UHFFFAOYSA-L 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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
- 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
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a process for preparing a polymer composition, characterized in that an ethylene based prepolymer (P) is obtained by polymerization in a prepolymerization zone in a slurry in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a first polymerization zone obtaining a first ethylene polymer component (a) by conducting polymerization in slurry in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a second polymerization zone a second ethylene polymer component (B) is obtained by polymerization carried out in slurry in the presence of ethylene, the first ethylene polymer component (a), optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a third polymerization zone obtaining a third ethylene polymer component (C) by polymerization in the gas phase in the presence of ethylene and at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, to produce a multimodal ethylene polymer (a) having at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, -wherein a) the density is from 900 to 960kg/m3B) MFR of 0.1 to 25g/10min2(measured at 190 ℃ under a load of 2.16kg according to ISO 1133), c) a MWD of 2 to 6, -which comprises at least-0.5 to<Between 7% by weight of an ethylene prepolymer (P) -10 to<Between 25 wt% of an ethylene polymer component (A), -10 to<Between 25% by weight of an ethylene polymer component (B) and->Between 51 and 79.5 wt% of an ethylene polymer component (C) and wherein the density of ethylene polymer components (A) and (B) is each 925 to 970kg/m3The density of the m-ethylene polymer component (C) is 880 to 950kg/m3Wherein further the ethylene polymer components (A), (B) and (C) have different MFR2The value is obtained.
Description
The present invention relates to a process for the preparation of a polymer composition, in particular for pipes, lids, closures, rotomoulded articles, artificial turf, geomembranes, blow moulded articles and/or mono-or multilayer films.
Various methods of preparing polymer compositions are currently known in the art. These methods include multi-stage processes so that the properties of the material can be fine-tuned, for example to improve the mechanical properties and/or processability or a balance of both.
In addition, the use of metallocene catalysts to improve optical properties, such as transparency and/or mechanical properties, is also known in the art.
However, especially good optical appearance remains a significant challenge. This challenge becomes more pronounced and urgent for materials that already have particularly good optical properties, in particular high transparency, since in this case even minor defects (e.g. gels) can have a significant negative effect on the optical appearance.
It is therefore an object of the present invention to improve the optical appearance of articles prepared with polymer compositions, in particular polymer compositions having high transparency and/or obtained with metallocene catalysts.
Accordingly, the present invention provides a process for preparing a polymer composition, wherein:
obtaining an ethylene based prepolymer (P) by polymerization in a prepolymerization zone in slurry in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a first polymerization zone obtaining a first ethylene polymer component (a) by conducting polymerization in slurry in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a second polymerization zone a second ethylene polymer component (B) is obtained by polymerization carried out in slurry in the presence of ethylene, the first ethylene polymer component (a), optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a third polymerization zone obtaining a third ethylene polymer component (C) by polymerization in the gas phase in the presence of ethylene and at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, to produce a multimodal ethylene polymer (a) having at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms,
-wherein,
a) the density is 900 to 960kg/m3In the above-mentioned manner,
b)0.1 toMFR of 25g/10min2(determined at 190 ℃ under a load of 2.16kg according to ISO 1133),
c) an MWD of from 2 to 6,
it at least comprises
Between 0.5 and < 7% by weight of an ethylene prepolymer (P)
-between 10 and <25 wt% of an ethylene polymer component (A),
between 10 and <25 wt% of an ethylene polymer component (B) and
- >51 to 79.5% by weight of an ethylene polymer component (C)
And wherein the ethylene polymer components (A) and (B) each have a density of 925 to 970kg/m3The density of the m-ethylene polymer component (C) is 880 to 950kg/m3Wherein further the ethylene polymer components (A), (B) and (C) have different MFR2The value is obtained.
The method according to the invention thus makes it possible to combine good optical properties, in particular high transparency, and/or good mechanical properties and/or good processability, with good optical appearance, in particular low defect levels, in particular low gel levels (in particular low gel levels of >1000 microns in size and/or 600-1000 microns in size and/or 300-599 microns in size and/or 100-299 microns in size). Thus, gels or defects may be caused in particular by crosslinked and/or high molecular weight polymer components. High transparency in the sense of the present invention can be obtained from, inter alia, metallocene LLDPE, for example, and/or can mean, for example, a light transmission of > 75%, preferably > 80%, in the visible spectrum.
Different MFR in the sense of the invention2The values may be, for example, values differing by 0.5, 0.1, 0.01, or even 0.001. The ethylene polymer components (a), (B) and (C) have different values of MFR2, which may thus mean that the multimodal ethylene polymer (a) may be e.g. bimodal or trimodal from the molecular weight point of view.
Thus, the Molecular Weight Distribution (MWD) corresponds to the Mw/Mn measured in a suitable manner by GPC.
The weight percentages (wt%) of the ethylene polymer components (a), (B) and (C) are given based on the weight of the polymer of the composition, i.e. the multimodal ethylene polymer (a), whereby at most >93 wt%, preferably >95 wt% or 100 wt% of the polymer, i.e. the multimodal ethylene polymer (a), is added to the polymer composition according to the invention. For the avoidance of doubt, this means that the weight percent (wt%) values of the ethylene polymer components (a), (B) and (C) may have to be selected, preferably within their respective ranges, such that the sum of their polymers in the polymer composition according to the invention, i.e. the multimodal ethylene polymer (a), is up to >93 wt%, preferably >95 wt% or 100 wt%.
In the process for preparing a polymer composition according to the present invention, the second ethylene polymer component (B) may preferably be obtained in the presence of the first ethylene polymer component (a), and/or the third ethylene polymer component (C) may be obtained in the presence of the first ethylene polymer component (a) and/or the second ethylene polymer component (B). However (in contrast to the second ethylene polymer component (B)), as used herein, the third ethylene polymer component (C) may preferably (only) refer to the component prepared in the third polymerization zone, and as such.
In the process for preparing a polymer composition according to the present invention, the ethylene-based prepolymer (P) and/or the first and/or second ethylene polymer components (a) and/or (B) may be obtained in the presence of 1-butene, 1-hexene and/or 1-octene as comonomer and/or the third ethylene polymer component (C) may be obtained in the presence of 1-butene, 1-hexene and/or 1-octene as comonomer. This may help to improve and/or optimize material properties, in particular optical and/or mechanical properties such as transparency.
In the process for preparing a polymer composition according to the present invention, the prepolymerization zone and/or the first and/or second polymerization zone may comprise at least one slurry loop reactor and the third polymerization zone comprises at least one gas phase reactor, preferably connected in series. This may help to improve and/or optimize material properties, in particular optical and/or mechanical properties such as transparency.
In the process for preparing a polymer composition according to the present invention, the ethylene prepolymer (P) and/or the first ethylene polymer component (a) may be prepared in a slurry loop reactor and the second ethylene polymer component (B) is prepared in a slurry loop reactor, preferably two or three slurry loop reactors connected in series. This may help to improve the homogeneity of the composition.
In the process for preparing a polymer composition according to the present invention, the first and second polymerization zones may each comprise a serially connected slurry loop reactor, hydrogen is fed to only the first of these slurry loop reactors, and the two slurry loop reactors are operated under identical/similar conditions or different conditions, preferably under identical/similar conditions, whereby preferably both slurry loop reactors are operated at a temperature between 70 and 95 ℃ and/or a pressure of 5000-. And/or the prepolymerization zone can be the smallest of the reactors used, whereby preferably the prepolymerization can be carried out at a temperature below the temperature in the first and/or second polymerization zone, preferably below the temperature of both slurry loop reactors, preferably in the range of 30 to 70 ℃ and/or the prepolymerization can be carried out at a pressure of 5000-6000kPa and/or the hydrogen concentration (in mol/kmol) in the prepolymerization zone can be the same as the hydrogen concentration (in mol/kmol) in the first polymerization zone. + -. 30%, preferably 20%, preferably 10%. Thus, similar conditions in the sense of the present invention may be conditions which deviate only by ± 25%, 20% or ± 10%, for example. Identical conditions in the sense of the present invention are identical conditions. Different conditions in the sense of the present invention may mean a difference > + -20%, preferably > + -25%. This may further contribute to improving the homogeneity of the composition.
In the process for preparing a polymer composition according to the present invention, the polymerization of the third ethylene polymer component (C) in the third polymerization zone is preferably carried out in the presence of at least one comonomer in the gas phase which is different from the comonomer present in the first and/or second polymerization zone, preferably to maximize the molecular weight and/or in the absence of hydrogen fed to the second polymerization zone. This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency.
In the process for preparing a polymer composition according to the present invention, the ethylene polymer component (A) may have a lower MFR than the ethylene polymer component (B)2Preferably 5 to 50, preferably 5 to 45, preferably 7 to 40, more preferably 10 to 30g/10min, further preferably 15 to 27g/10min, and/or the ethylene polymer component (B) may have an MFR of 5-50g/10min2Preferably from 5 to 45, preferably from 7 to 40, more preferably from 10 to 35g/10min, further preferably from 15 to 34g/10min and/or wherein the MFR of the ethylene polymer component (C)5May be from 0.01 to 5, preferably from 0.05 to 3, preferably from 0.5 to<2g/10min, both determined according to ISO1133 at 190 ℃ under a load of 2.16kg or 5kg and/or wherein the prepolymer may have an MFR in the range from 5 to 502Preferably with the MFR of the first ethylene polymer component2The same. + -. 40%, preferably. + -. 30%, preferably. + -. 20%, preferably. + -. 10%. This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency. Furthermore, this may also help to improve the homogeneity of the composition.
In the process for preparing a polymer composition according to the present invention, the alpha-olefin comonomer having 4 to 10 carbon atoms of the ethylene polymer components (a) and (B) may be 1-butene and the alpha-olefin comonomer having 4 to 10 carbon atoms of the ethylene polymer component (C) may be 1-hexene and/or the multimodal ethylene polymer (a) may comprise between 15 and 24 wt%, preferably between 17 and <24 wt% of the ethylene polymer components (a) and (B) and/or between >51 and 65, preferably between 55 and <65 wt%, between 52 and 63 wt%, preferably between >52 and <63 wt% or between >50 and <60 wt% of the ethylene polymer component (C). This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency.
In the process for preparing a polymer composition according to the present invention, the density of the ethylene polymer component (B) may be equal to or lower than the density of the ethylene polymer component (a). This may help to improve the homogeneity of the composition and/or further improve the optical appearance.
In the process for preparing a polymer composition according to the present invention, the density of the ethylene component (C) is equal to or lower than the density of the ethylene polymer component (a) and/or the ethylene polymer component (B). This may help to improve the homogeneity of the composition and/or further improve the optical appearance.
In the process for preparing a polymer composition according to the present invention, the density of the ethylene polymer components (a) and (B) may be 930 to 945, preferably 931 to 945>931 to<945, preferably 935 to 945kg/m3And/or the density of the polymer component (C) may be 905 to 955, preferably 910 to 940, preferably 915 to 950, further preferably 925 to 945 or 930 to 942kg/m3Or 945 to 965, preferably 950 to 965<965kg/m3And/or the density of the polymer component (C) may be 920 to 945, preferably 925 to 925<945, preferably 930 to 945<945kg/m3. This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency. Furthermore, this may also help to improve the homogeneity of the composition.
In the process for preparing a polymer composition according to the invention, the density of the multimodal ethylene polymer (a) may be 915 to 955, preferably 930 to 950kg/m3And/or MFR of the multimodal ethylene polymer (a)2May be between 0.1 and 10, preferably between 0.5 and 8, preferably between 0.6 and 3g/10min and/or wherein the multimodal ethylene polymer (a) may have an MFR of 10 to 4021/MFR2Preferably 15 to 35, preferably 20 to 35<35, preferably of>25 to<35 and/or the multimodal ethylene polymer (a) has an MFR of 1 to 55Preferably is>1 to<3g/10 min. This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency
In the process for preparing the polymer composition according to the invention the multimodal ethylene polymer (a) may contain gels having a size of 600-1000 microns per square meter with a gel number of >0 to 150 or less, preferably less than 100, preferably less than 75, preferably less than 60 and/or the multimodal ethylene polymer (a) has gels having a size of 300-599 microns per square meter with a gel number of >0 to 1500 or less, preferably less than 1450, 1400 or less and/or wherein the multimodal ethylene polymer (a) may have gels with a size >1000 micron per square meter with a gel number of 0 to 2 or less, preferably 1 or less and/or the multimodal ethylene polymer (a) may have gels with a size of 100-299 micron with a gel number of >0 to 70000 or less, preferably 40000 or less, preferably 20000 or less. This may help to further improve the optical appearance.
In the process for preparing a polymer composition according to the present invention the multimodal ethylene polymer (a) may be prepared using a single site catalyst, preferably a substituted and/or bridged bis-cyclopentadienyl zirconium or hafnium catalyst and/or preferably (a), (B) and (C) in the multimodal ethylene polymer (a) may be prepared using the same single site catalyst, preferably a substituted and/or bridged bis-cyclopentadienyl zirconium or hafnium catalyst, and/or each having a MWD of between 2.0 and 5.0, preferably between 2.5 and 4.5, preferably >2.5 to < 4.0. This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency. Furthermore, this also contributes to an improved homogeneity and/or optical appearance of the composition.
The invention also relates to pipes, lids, closures, rotomoulded articles, artificial turf mats, geomembranes, blow moulded articles and/or mono-or multilayer films comprising a polymer composition prepared using the process according to the invention. Such articles may show good optical properties, especially high transparency, and/or good mechanical properties and/or good processability with good optical appearance, especially low defect levels, especially low gel levels, especially low levels of gels having a size of >1000 microns and/or a size of 600-1000 microns and/or a size of 300-599 microns and/or a size of 100-299 microns. This may help to improve the optical appearance.
To prepare the polymer composition, for example in the present invention, two or more reactors or zones connected in series as described in EP517868, which is hereby incorporated by reference in its entirety, may be used.
According to the present invention, the main polymerization stage is preferably operated as a combination of slurry polymerization/gas phase polymerization. Slurry polymerization is preferably carried out in a so-called slurry loop reactor.
Optionally, the main polymerization stage may be preceded by a prepolymerization, in which case the ethylene based prepolymer (P) may be prepared in an amount of, for example, 0.1 to <7 wt%, preferably 0.1 to < wt 5%, preferably 1 to 4 wt%, based on the total amount of polymer. The prepolymer may be an ethylene homopolymer or copolymer, preferably an ethylene copolymer, further preferably 1-butene.
In case of a prepolymerization, the weight percentages (wt%) of the ethylene polymer components (a), (B) and (C) are given based on the weight of the polymer composition, i.e. the multimodal ethylene polymer (a), thus up to >93 wt%, preferably >95 wt% of the polymer, i.e. the multimodal ethylene polymer (a), is added to the polymer composition according to the invention, such that the weight percentages (wt%) of the ethylene polymer components (a), (B), (C) and the prepolymer (P) have to be selected within their respective ranges to add up to 100 wt% based on the weight of the polymer, i.e. the multimodal ethylene polymer (a). This may further contribute to improving and/or optimizing material properties, in particular optical and/or mechanical properties such as transparency. Furthermore, this also contributes to an improved homogeneity and/or optical appearance of the composition.
If a prepolymerization takes place, in this case it is preferred that all the catalyst is charged in the first prepolymerization reactor and that the prepolymerization is carried out as a slurry polymerization. This polymerization results in less fines being produced in the subsequent reactor and ultimately a more uniform product.
The resulting multimodal polymer of ethylene (a) consists of an intimate mixture of polymers from the three main reactors, the different molecular weight distribution curves of these polymers together forming a molecular weight distribution curve with a broad maximum or three maxima, i.e. the final product is a trimodal polymer mixture.
The polymer composition according to the invention may also comprise additives such as processing aids, antioxidants, pigments, UV-stabilizers and the like. Typically, the amount of those additives may be from 0 to 10 wt% or >0 to 10 wt%, based on the weight of the total composition. This means that the amount of polymer in the polymer composition, i.e. the multimodal ethylene polymer (a), may be from 90 wt% to 100 wt% or from 90 wt% to < 100 wt%.
Examples
Three samples CE1, CE2, and IE were prepared using prepolymerization followed by polymerization in a first slurry reactor (loop reactor 1) by feeding ethylene (C2), one metallocene catalyst as described below, 1-butene (C4) as comonomer, hydrogen, and propane as diluent. The first slurry loop reactor is then connected in series with another slurry reactor (loop reactor 2) such that the first ethylene polymer component (a) produced in loop reactor 1 is fed to loop reactor 2. Whereby ethylene is polymerized in the presence of the polymer produced in the loop reactor 1, 1-butene (C4) as comonomer and hydrogen to produce the second ethylene component (B). The loop reactor 2 is thus connected in series to a Gas Phase Reactor (GPR) such that the second ethylene component (B) is fed to the GPR and ethylene is polymerized in the GPR with 1-hexene (C6) as comonomer and hydrogen to yield the third ethylene polymer component (C), i.e. to produce the multimodal ethylene polymer (a).
The process comprises a flash between the loop reactor 2 and the GPR reactor to remove diluent and unreacted monomers.
The polymerization conditions are given in table 1 below.
The MWD of each sample was in the range of 2-6 as determined by GPC. Similarly, the MWD of each ethylene polymer component is determined by GPC to be in the range of 2 to 4.
Preparing a catalyst:
130 g of the metallocene complex bis (1-methyl-3-n-butylcyclopentadienyl) zirconium (IV) dichloride (CAS number 151840-68-5) and 9.67kg of a 30% solution of commercial Methylaluminoxane (MAO) in toluene were combined and 3.18kg of dry purified toluene were added. The resulting complex solution was then added to 17kg of silica carrier Sylopol55SJ (supplied by Grace) by a very slow uniform spray over 2 hours. The temperature was kept below 30 ℃. After addition of the complex, the mixture was allowed to react at 30 ℃ for 3 hours.
Molecular weight, molecular weight distribution, Mn, Mw, MWD:
weight average molecular weight Mw and molecular weight distribution (MWD ═ Mw/Mn, where Mn is the number average molecular weight and Mw is the weight average molecular weight) are determined by a method based on ISO 16014-4: 2003. A Waters150CVplus instrument equipped with a refractive index detector and an in-line viscometer was used with a 3XHT6E polystyrene gel column from Waters (styrene-divinylbenzene) and 1,2, 4-trichlorobenzene (TCB stabilized with 250mg/L2, 6-di-tert-butyl-4-methylphenol) as solvent at 140 ℃ and at a constant flow rate of 1 mL/min. 500 μ L of sample solution was injected for each analysis. The column set was calibrated with 10 narrow MWD Polystyrene (PS) standards using a universal calibration (according to ISO16014-2:2003) in the range of 1.05kg/mol to 11600 kg/mol. Mark Houwink constants were used for polystyrene and polyethylene (PS: K: 19X 10)-3dL/g and a: 0.655; and for PE, K: 39x10-3dL/g and a: 0.725). All samples were prepared by dissolving 0.5-3.5mg of polymer in 4mL (at 140 ℃) of stable TCB (same as the mobile phase) and holding at 140 ℃ for 2 hours, at 160 ℃ for another 2 hours, with occasional shaking before sampling on the GPC instrument.
Gel content:
the gel content was analyzed by an optical control system (OCS Film-Test FSA100) and a CCD (charge coupled device) camera provided by an optical control system GmbH, which determined gels and defects in films prepared from the compositions. Gels and defects are identified electro-optically by their different light transmittance compared to thin film substrates.
A translucent 70 μm thick cast film was photographed using a high resolution line camera and appropriate background illumination. The amount and area of gel per total film area was then calculated using image recognition software.
Film defects/gels were determined and classified according to their size (longest dimension).
Preparation of cast film, extrusion parameters:
1. output 25 +/-4 g/min
2. Extruder temperature profile 200/210/210/210/210-end
3. Film thickness of about 70pm
4. The temperature of the cooling roller is 20 DEG C
5. Require an air knife
Extruder technical data:
1. the screw type: 3 stage (iii) nitration
2. Screw diameter: 25mm
3. Length of screw: 25D
4. A feeding section: 10D
5. A compression section: 4D
6. End 150mm
Defects were classified according to size (pm)/m 2:
100-299
300-599
600-999
>1000
the results are also shown in table 1 below. It can be seen that the gel number of IE is reduced and the optical appearance is improved compared to CE1 and CE 2.
TABLE 1
Claims (15)
1. A process for the preparation of a polymer composition, characterized in that a vinyl prepolymer (P) is obtained in a prepolymerization zone by polymerization in a slurry in the presence of ethylene, optionally at least one comonomer selected from α -olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a first polymerization zone obtaining a first ethylene polymer component (a) by polymerization in slurry in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a second polymerization zone a second ethylene polymer component (B) is obtained by polymerization carried out in slurry in the presence of ethylene, the first ethylene polymer component (a), optionally at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, and optionally hydrogen; and in a third polymerization zone obtaining a third ethylene polymer component (C) by polymerization in the gas phase in the presence of ethylene and at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms, to produce a multimodal ethylene polymer (a) having at least one comonomer selected from alpha-olefins having from 4 to 10 carbon atoms,
-wherein,
a) the density is 900 to 960kg/m3In the above-mentioned manner,
b) MFR of 0.1 to 25g/10min2(determined at 190 ℃ under a load of 2.16kg according to ISO 1133),
c) an MWD of from 2 to 6,
it at least comprises
Between 0.5 and < 7% by weight of an ethylene prepolymer (P)
-between 10 and <25 wt% of an ethylene polymer component (A),
between 10 and <25 wt% of an ethylene polymer component (B) and
- >51 to 79.5% by weight of an ethylene polymer component (C)
And wherein the ethylene polymer components (A) and (B) each have a density of 925 to 970kg/m3The density of the m-ethylene polymer component (C) is 880 to 950kg/m3Wherein further the ethylene polymer components (A), (B) and (C) have different MFR2The value is obtained.
2. The process for preparing a polymer composition according to claim 1, wherein the ethylene prepolymer (P) and/or the first and/or second ethylene polymer component (a) and/or (B) is obtained in the presence of 1-butene, 1-hexene and/or 1-octene as comonomer and/or the third ethylene polymer component (C) is obtained in the presence of 1-butene, 1-hexene and/or 1-octene as comonomer.
3. Process for preparing a polymer composition according to claim 1 or 2, characterized in that the prepolymerization zone and/or the first and/or second polymerization zone comprise(s) at least one slurry loop reactor and the third polymerization zone comprises(s) at least one gas phase reactor, preferably connected in series.
4. The process for preparing a polymer composition according to any of the preceding claims, wherein the ethylene prepolymer (P) and/or the first ethylene polymer component (a) is prepared in a slurry loop reactor and the second ethylene polymer component (B) is prepared in a slurry loop reactor, preferably two or three slurry loop reactors are connected in series.
5. Process for preparing a polymer composition according to any of the preceding claims, characterized in that the first and second polymerization zones each comprise a slurry loop reactor connected in series, hydrogen is fed to only the first of these slurry loop reactors and the two slurry loop reactors are operated under identical/similar conditions or different conditions, preferably under identical/similar conditions, preferably the two slurry loop reactors are operated at a temperature between 70 and 95 ℃ and/or a pressure of 5000-6000kPa, and/or preferably both slurry loop reactors are operated at the same temperature ± 10% or ± 5 ℃ and/or the same pressure ± 10% or ± 50kPa and/or the prepolymerization zone is the smallest of the reactors used, whereby preferably the prepolymerization is carried out at a temperature lower than the temperature in the first and/or second polymerization zone, preferably at a temperature below the temperature of the two slurry loop reactors, preferably in the range of from 30 to 70 ℃ and/or the prepolymerization is carried out at a pressure of 5000-6000kPa and/or the hydrogen concentration (in mol/kmol) in the prepolymerization zone is the same as the hydrogen concentration (in mol/kmol) in the first polymerization zone. + -. 30%, preferably. + -. 20%, preferably. + -. 10%.
6. Process for preparing a polymer composition according to any one of the preceding claims, wherein the polymerization of the third ethylene polymer component (C) in the third polymerization zone is preferably carried out in the presence of at least one comonomer in the gas phase which is different from said comonomer present in said first and/or second polymerization zone, preferably to maximize the molecular weight and/or in the absence of hydrogen fed to said second polymerization zone.
7. The process for preparing a polymer composition according to any of the preceding claims, wherein the ethylene polymer component (A) has a lower MFR than the ethylene polymer component (B)2Preferably 5 to 50, preferably 5 to 45, preferably 7 to 40, more preferably 10 to 30g/10min, further preferably 15 to 27g/10min, and/or the ethylene polymer component (B) has an MFR of 5 to 50g/10min2Preferably from 5 to 45, preferably from 7 to 40, more preferably from 10 to 35g/10min, further preferably from 15 to 34g/10min and/or wherein the MFR of the ethylene polymer component (C)5Is 0.01 to 5, preferably 0.05 to 3, preferably 0.5 to 5<2g/10min, both determined according to ISO1133 at 190 ℃ under a load of 2.16kg or 5kg and/or wherein the prepolymer has an MFR in the range from 5 to 502Preferably with the MFR of the first ethylene polymer component2The same. + -. 40%, preferably. + -. 30%, preferably. + -. 20%, preferably. + -. 10%.
8. The process for preparing a polymer composition according to any of the preceding claims wherein the alpha-olefin comonomer having 4 to 10 carbon atoms of ethylene polymer components (a) and (B) is 1-butene and the alpha-olefin comonomer having 4 to 10 carbon atoms of ethylene polymer component (C) is 1-hexene and/or wherein the multimodal ethylene polymer (a) comprises between 15 and 24, preferably between 17 and <24 wt% of ethylene polymer component (a) and/or (B) and/or preferably between 52 and 63 wt%, preferably between >52 and <63 or >50 to <60 wt% of ethylene polymer component (C).
9. The process for preparing a polymer composition according to any of the preceding claims, wherein the density of the ethylene polymer component (B) is equal to or lower than the density of the ethylene polymer component (A).
10. The process for preparing a polymer composition according to any of the preceding claims, wherein the density of the ethylene component (C) is equal to or lower than the density of the ethylene polymer component (A) and/or the ethylene polymer component (B).
11. The process for preparing a polymer composition according to any of the preceding claims, wherein the ethylene polymer components (A) and (B) have a density of 930 to 945, preferably 931 to 945, preferably are>931 to<945, preferably 935 to 945kg/m3And/or the density of the polymer component (C) is 905 to 955, preferably 910 to 940, preferably 915 to 950, further preferably 925 to 945 or 930 to 942kg/m3Or 945 to 965, preferably 950 to 965<965kg/m3And/or the density of the polymer component (C) is 920 to 945, preferably 925 to 925<945, preferably 930 to 945<945kg/m3。
12. The process for preparing a polymer composition according to any preceding claim wherein the multimodal ethylene polymer (a) has a density of 915 to 955, preferably 930 to 950, kg/m3And/or wherein the MFR2 of the multimodal ethylene polymer (a) is between 0.1 and 10, preferably between 0.5 and 8, preferably between 0.6 and 3g/10min and/or wherein the multimodal ethylene polymer (a) has a MFR21/MFR2 of 10 to 40, preferably between 15 and 35, preferably between 20 and 20<35, preferably of>25 to<35 and/or wherein the multimodal ethylene polymer (a) has an MFR5 of 1 to 5, preferably of>1 to<3g/10min。
13. The process for preparing a polymer composition according to any of the preceding claims, wherein the multimodal ethylene polymer (a) contains gels having a size of 600-1000 microns per square meter, the number of gels is from 0 to 150 or less, preferably less than 100, preferably less than 75, preferably less than 60 and/or the multimodal ethylene polymer (a) has gels having a size of 300-599 microns per square meter, the number of gels is from >0 to 1500 or less, preferably 1450 or less, 1400 or less and/or wherein the multimodal ethylene polymer (a) may have gels having a size of >1000 microns per square meter, the number of gels is from 0 to 2 or less, preferably 1 or less and/or the multimodal ethylene polymer (a) may have gels having a size of 100-299-microns, the number of gels is from >0 to 70000 or less, preferably 40000 or less, preferably 20000 or less.
14. The process for preparing a polymer composition according to any of the preceding claims, wherein the multimodal ethylene polymer (a) is prepared using a single site catalyst, preferably a substituted and/or bridged bis-cyclopentadienyl zirconium or hafnium catalyst and/or preferably (A), (B) and (C) in the multimodal ethylene polymer are prepared using the same single site catalyst, preferably a substituted and/or bridged bis-cyclopentadienyl zirconium or hafnium catalyst and/or each have a MWD of between 2.0 and 5.0, preferably between 2.5 and 4.5, preferably between >2.5 and <4.
15. A pipe, lid, closure, rotomoulded article, artificial turf mat, geomembrane, blow moulded article and/or mono-or multilayer film comprising the polymer composition prepared using the method according to any one of the preceding claims 1 to 14.
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| EP19186849 | 2019-07-17 | ||
| PCT/EP2020/069927 WO2021009190A1 (en) | 2019-07-17 | 2020-07-15 | Process for producing a polymer composition |
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| CN109922960A (en) * | 2016-11-25 | 2019-06-21 | 博里利斯股份公司 | The preparation method of polyolefin film composition and the film being made from it |
| CN109963713A (en) * | 2016-11-25 | 2019-07-02 | 博里利斯股份公司 | The preparation method of polyolefin film composition and the film being made from it |
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| Publication number | Publication date |
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| CN114364735B (en) | 2024-04-26 |
| EP3999566A1 (en) | 2022-05-25 |
| WO2021009190A1 (en) | 2021-01-21 |
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