CN114364735B - Method for preparing polymer composition - Google Patents
Method for preparing polymer composition Download PDFInfo
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- CN114364735B CN114364735B CN202080062123.1A CN202080062123A CN114364735B CN 114364735 B CN114364735 B CN 114364735B CN 202080062123 A CN202080062123 A CN 202080062123A CN 114364735 B CN114364735 B CN 114364735B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 121
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005977 Ethylene Substances 0.000 claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 239000004711 α-olefin Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 101100023124 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfr2 gene Proteins 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 description 27
- 239000000463 material Substances 0.000 description 11
- 230000007547 defect Effects 0.000 description 7
- 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
- 230000005540 biological transmission Effects 0.000 description 2
- 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 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002356 single layer Substances 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
- 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
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 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
- 238000005259 measurement Methods 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
- 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
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- 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
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- 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
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- 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)
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- 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 in a prepolymerization zone by polymerization in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms and optionally hydrogen in a slurry; and obtaining a first ethylene polymer component (a) by polymerization in a slurry in a first polymerization zone in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms, and optionally hydrogen; and obtaining a second ethylene polymer component (B) in a second polymerization zone by polymerization in the presence of ethylene, a first ethylene polymer component (a), optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms and optionally hydrogen, in a slurry; and obtaining a third ethylene polymer component (C) in a third polymerization zone by polymerization in the gas phase in the presence of ethylene and at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms, to produce a multimodal ethylene polymer (a) having at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms, -wherein a) has a density of between 900 and 960kg/m 3, B) has an MFR 2 of 0.1 to 25g/10min (measured at 190 ℃ under a load of 2.16kg according to ISO 1133), C) 2 to 6, -it comprises at least an ethylene prepolymer (P) of between-0.5 and <7wt% of an ethylene polymer component (a), -an ethylene polymer component (B) of between 10 and <25wt% and an ethylene polymer component (C) of between-51 and 79.5wt%, and wherein the densities of the ethylene polymer components (a) and (B) are each between 925 and 970kg/m 3, and the ethylene polymer component (C) has an MWD of between-0.5 and <7wt% and <25wt%, and wherein the ethylene polymer component (C) has a density of between 880 and 32 kg/32.82, and a further has different values.
Description
The present invention relates to a process for preparing a polymer composition, in particular for pipes, caps, closures, rotomoulded articles, artificial grass mats, geomembranes, blow moulded articles and/or single-layer or multi-layer films.
Currently, various methods of preparing polymer compositions are known in the art. These methods include multi-stage processes that allow fine tuning of the properties of the material, for example to improve 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, especially high transparency, because in this case even minor imperfections (e.g. gels) can have a significant negative impact 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.
Thus, the present invention provides a process for preparing a polymer composition, wherein:
Obtaining an ethylene-based prepolymer (P) by polymerization in a slurry in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms, and optionally hydrogen in a prepolymerization zone; and obtaining a first ethylene polymer component (a) by polymerization in a slurry in a first polymerization zone in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms, and optionally hydrogen; and obtaining a second ethylene polymer component (B) in a second polymerization zone by polymerization in the presence of ethylene, a first ethylene polymer component (a), optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms and optionally hydrogen, in a slurry; and obtaining a third ethylene polymer component (C) in a third polymerization zone by polymerization in the gas phase in the presence of ethylene and at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms to produce a multimodal ethylene polymer (a) having at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms,
-Wherein the first and second heat exchangers are arranged in parallel,
A) The density is between 900 and 960kg/m 3,
B) An MFR 2 (measured according to ISO 1133 at 190 ℃ C. Under a load of 2.16 kg) of 0.1 to 25g/10min,
C) A MWD of 2 to 6,
It at least comprises
-Between 0.5 and <7wt% of a vinyl prepolymer (P)
Between 10 and <25 wt.% of an ethylene polymer component (A),
-Between 10 and <25wt% of an ethylene polymer component (B) and
- > Between 51 and 79.5% by weight of an ethylene polymer component (C)
And wherein the densities of the ethylene polymer components (A) and (B) are each between 925 and 970kg/m 3 and the density of the ethylene polymer component (C) is between 880 and 950kg/m 3, wherein further the ethylene polymer components (A), (B) and (C) have different MFR 2 values.
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 dimensions >1000 microns and/or dimensions 600-1000 microns and/or dimensions 300-599 microns and/or dimensions 100-299 microns). 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 may be obtained, inter alia, by, for example, metallocene LLDPE, and/or may mean, for example, a light transmission of >75%, preferably >80%, in the visible spectrum.
Thus the different values of MFR 2 in the sense of the present invention 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 MFR2 values, which may thus mean that the multimodal ethylene polymer (a) may be bimodal or trimodal from a molecular weight point of view, for example.
Thus, the Molecular Weight Distribution (MWD) corresponds to the Mw/Mn measured by GPC in a suitable manner.
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 up to >93wt%, preferably >95wt% or 100wt% 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 it may be necessary to select the weight percent (wt%) values of the ethylene polymer components (a), (B) and (C), preferably within their respective ranges, so that their polymers in the polymer composition according to the invention, i.e. the sum of the multimodal ethylene polymers (a), is up to >93wt%, preferably >95wt% or 100wt%.
In the process for preparing a polymer composition according to the 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 (as compared to the second ethylene polymer component (B)), as used herein, the third ethylene polymer component (C) may preferably refer to (only) the components produced in the third polymerization zone, such that.
In the process for preparing a polymer composition according to the invention, the ethylene-based prepolymer (P) and/or the first and/or second ethylene polymer component (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 properties such as transparency and/or mechanical properties.
In the process for preparing a polymer composition according to the invention, the prepolymerization zone and/or the first and/or the 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 properties such as transparency and/or mechanical properties.
In the process for preparing a polymer composition according to the invention, the ethylene-based 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 invention, the first and second polymerization zone may each comprise a series connected slurry loop reactor, hydrogen being fed to only a first one 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 5000-6000kPa, and/or preferably both slurry loop reactors are operated at the same temperature + -10% or + -5 ℃ and/or the same pressure + -10% or + -50 kPa. And/or the prepolymerization zone may be the smallest of the reactors used, whereby preferably the prepolymerization may be carried out at a temperature lower than the temperature in the first and/or second polymerization zone, preferably at a temperature lower than two slurry loop reactors, preferably in the range of 30 to 70 ℃ and/or the prepolymerization may be carried out at a pressure of 5000-6000kPa and/or the hydrogen concentration (in mol/kmol) in the prepolymerization zone may be the same as the hydrogen concentration (in mol/kmol) in the first polymerization zone by + -30%, preferably + -20%, preferably + -10%. Thus, similar conditions in the sense of the present invention may be, for example, conditions that deviate by only + -25%, + -20% or + -10%. The same conditions in the sense of the present invention are identical conditions. Different conditions in the sense of the present invention may mean a difference of >.+ -. 20%, preferably >.+ -. 25%. This may further help to improve the homogeneity of the composition.
In the process for preparing a polymer composition according to the invention, the polymerization of the third ethylene polymer component (C) in the third polymerization zone is preferably carried out in the gas phase in the presence of at least one comonomer different from the comonomer present in the first and/or second polymerization zone, preferably to maximize said molecular weight and/or in the absence of hydrogen fed to the second polymerization zone. This may further help to improve and/or optimize material properties, in particular optical properties such as transparency and/or mechanical properties.
In the process for preparing a polymer composition according to the invention, the ethylene polymer component (a) may have a lower MFR 2, preferably from 5 to 50, preferably from 5 to 45, preferably from 7 to 40, more preferably from 10 to 30g/10min, further preferably from 15 to 27g/10min, than the ethylene polymer component (B), and/or the ethylene polymer component (B) may have a MFR 2 of from 5 to 50g/10min, preferably 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 5 of the ethylene polymer component (C) may be from 0.01 to 5, preferably from 0.05 to 3, preferably from 0.5 to <2g/10min, all measured according to ISO1133 at 190 ℃ under a load of 2.16kg or 5kg and/or wherein the prepolymer may have a MFR 2 in the range of from 5 to 50, preferably from 10 to 35g/10min, further preferably from 15 to 34 ± 20% preferably being the same as 34 ± 20% preferably as the first ethylene polymer component. This may further help to improve and/or optimize material properties, in particular optical properties such as transparency and/or mechanical properties. In addition, this may also help to improve the homogeneity of the composition.
In the process for preparing a polymer composition according to the 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 to 24wt%, preferably between 17 to <24wt% of the ethylene polymer components (a) and (B) and/or between >51 to 65, preferably between 55 to <65wt%, between 52 to 63wt%, preferably between >52 to <63wt% or >50 to <60wt% of the ethylene polymer component (C). This may further help to improve and/or optimize material properties, in particular optical properties such as transparency and/or mechanical properties.
In the method for producing 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 method for producing 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 invention, the ethylene polymer components (a) and (B) may have a density of 930 to 945, preferably 931 to 945, preferably >931 to <945, preferably 935 to 945kg/m 3 and/or the polymer component (C) may have a density of 905 to 955, preferably 910 to 940, preferably 915 to 950, further preferably 925 to 945 or 930 to 942kg/m 3 or 945 to 965, preferably 950 to <965kg/m 3 and/or the polymer component (C) may have a density of 920 to 945, preferably 925 to <945, preferably 930 to <945kg/m 3. This may further help to improve and/or optimize material properties, in particular optical properties such as transparency and/or mechanical properties. In addition, 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/m 3 and/or the MFR 2 of the multimodal ethylene polymer (a) may 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 21/MFR2 of 10 to 40, preferably 15 to 35, preferably 20 to <35, preferably >25 to <35 and/or the multimodal ethylene polymer (a) has an MFR 5 of 1 to 5, preferably >1 to <3g/10min. This may further contribute to improving and/or optimizing material properties, in particular optical properties such as transparency and/or mechanical properties
In the process for preparing a polymer composition according to the invention, the multimodal ethylene polymer (a) may contain a gel having a size of 600-1000 micrometers per square meter with a gel number of >0 to 150, preferably below 100, preferably below 75, preferably below 60 and/or the multimodal ethylene polymer (a) has a gel having a size of 300-599 micrometers per square meter with a gel number of >0 to 1500, preferably 1450 or less, 1400 or less and/or wherein the multimodal ethylene polymer (a) may have a gel having a size of >1000 micrometers per square meter with a gel number of 0 to 2, preferably 1 or less and/or the multimodal ethylene polymer (a) may have a gel having a size of 100-299 micrometers per square meter with a gel number of >0 to 70000, preferably 40000 or less, preferably 20000 or less. This may help to further improve the optical appearance.
In the process for preparing the polymer composition according to the 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 have 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 help to improve and/or optimize material properties, in particular optical properties such as transparency and/or mechanical properties. In addition, this also helps to improve the homogeneity and/or optical appearance of the composition.
The invention also relates to pipes, caps, closures, rotomoulded articles, artificial grass mats, geomembranes, blow moulded articles and/or single-layer or multi-layer films comprising a polymer composition prepared using the method according to the invention. Such articles may exhibit 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 levels of gels having a size >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.
For the preparation of the polymer composition, for example in the present invention, two or more reactors or zones connected in series as described in EP517868 may be used, which is incorporated herein by reference in its entirety.
According to the invention, the main polymerization stage is preferably operated for a combination of slurry polymerization/gas phase polymerization. The 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 <7wt%, preferably 0.1 to < 5 wt%, preferably 1 to 4wt%, based on the weight of the total polymer. The prepolymer may be an ethylene homo-or copolymer, preferably an ethylene copolymer, further preferably 1-butene.
In the presence 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), whereby up to >93wt%, preferably >95wt%, 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 be added up to 100wt%, based on the weight of the polymer, i.e. the multimodal ethylene polymer (a). This may further help to improve and/or optimize material properties, in particular optical properties such as transparency and/or mechanical properties. In addition, this also helps to improve the homogeneity and/or optical appearance of the composition.
If prepolymerization occurs, in this case, it is preferable to charge all the catalyst into the first prepolymerization reactor and the prepolymerization is carried out as slurry polymerization. This polymerization results in less fines generation in the subsequent reactors and ultimately a more uniform product.
The resulting ethylene multimodal polymer (a) consists of an intimate mixture of polymers from three main reactors, the different molecular weight distribution curves of these polymers together forming a molecular weight distribution curve having a broad 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, etc. Typically, those additives may be present in amounts of 0 to 10wt% or > 0 to 10wt% 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 to 100wt% or from 90 to < 100wt%.
Examples
Three samples CE1, CE2, and IE were prepared using prepolymerization followed by polymerization in a first slurry reactor (loop reactor 1) with ethylene (C2), a 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) so that the first ethylene polymer component (a) prepared in the loop reactor 1 is fed into the 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) whereby 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 obtain the third ethylene polymer component (C), i.e. to produce the multimodal ethylene polymer (a).
The process comprises flash distillation between loop reactor 2 and the GPR reactor to remove diluent and unreacted monomer.
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.
And (3) 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% commercial Methylaluminoxane (MAO) in toluene were combined and 3.18kg of dry purified toluene was added. The resulting complex solution was then added to 17kg of silica support Sylopol55SJ (supplied by Grace) by a very slow uniform spray for more than 2 hours. The temperature is kept below 30 ℃. After the complex was added, 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, mw is the weight average molecular weight) by being based on ISO16014-4:2003, method of measurement. Waters150CVplus instrument equipped with refractive index detector and 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. Mu.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 ISO 16014-2:2003) in the range of 1.05kg/mol to 11600 kg/mol. Mark Houwink constants were used for polystyrene and polyethylene (PS: K:19x10 -3 dL/g and a:0.655; and for PE, K:39x10 -3 dL/g and a: 0.725). All samples were prepared by dissolving 0.5-3.5mg of polymer in 4mL (140 ℃ C.) of stabilized TCB (same mobile phase) and holding at 140 ℃ for 2 hours and 160 ℃ for another 2 hours, with occasional shaking prior to sampling by GPC equipment.
Gel content:
The gel content was analyzed by an optical control system (OCS Film-Test FSA 100) and a CCD (charge coupled device) camera provided by an optical control system GmbH, which determines gels and defects in films prepared from the composition. Gels and defects are photoelectrically identified by their different light transmission compared to film substrates.
A translucent 70 μm thick cast film was photographed using a high resolution line camera and appropriate background illumination. The gel quantity and area per total film area was then calculated using image recognition software.
Film defects/gels were determined and classified according to their size (minimum size).
Preparation of cast film, extrusion parameters:
1. output 25+ -4 g/min
2. Extruder temperature profile 200/210/210/210/210-termination
3. Film thickness about 70pm
4. The temperature of the cooling roller is 20 DEG C
5. Air knife
Extruder technical data:
1. screw model: 3 stage, nitration
2. Screw diameter: 25mm of
3. Screw length: 25D (25D)
4. And (3) a feeding section: 10D (10D)
5. Compression section: 4D (4D)
6. Terminating 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 count of IE is reduced and the optical appearance is improved compared to CE1 and CE 2.
TABLE 1
Claims (18)
1. A process for preparing a polymer composition, characterized in that a vinyl prepolymer (P) is obtained in a prepolymerization zone by polymerization in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms and optionally hydrogen in a slurry; and obtaining a first ethylene polymer component (a) by polymerization in a slurry in a first polymerization zone in the presence of ethylene, optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms, and optionally hydrogen; and obtaining a second ethylene polymer component (B) in a second polymerization zone by polymerization in the presence of ethylene, a first ethylene polymer component (a), optionally at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms and optionally hydrogen, in a slurry; and obtaining a third ethylene polymer component (C) in a third polymerization zone by polymerization in the gas phase in the presence of ethylene and at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms to produce a multimodal ethylene polymer (a) having at least one comonomer selected from alpha-olefins having 4 to 10 carbon atoms,
-Wherein the first and second heat exchangers are arranged in parallel,
A) The density is between 900 and 960kg/m 3,
B) MFR 2 measured according to ISO 1133 at 190℃under a load of 2.16kg of 0.1 to 25g/10min,
C) A MWD of 2 to 6,
It at least comprises
-Between 0.5 and <7wt% of a vinyl prepolymer (P)
Between 10 and <25 wt.% of an ethylene polymer component (A),
-Between 10 and <25wt% of an ethylene polymer component (B) and
- > Between 51 and 79.5% by weight of an ethylene polymer component (C)
And wherein the densities of the ethylene polymer components (a) and (B) are each between 925 and 970kg/m 3, wherein the density of the ethylene polymer component (B) is equal to or lower than the density of the ethylene polymer component (a), and the density of the ethylene polymer component (C) is between 880 and 950kg/m 3, wherein further the ethylene polymer components (a), (B) and (C) have different MFR 2 values.
2. The process for preparing a polymer composition according to claim 1, characterized in that the ethylene-based 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. The process for preparing a polymer composition according to claim 1, characterized in that the prepolymerization zone and/or the first and/or the second polymerization zone comprise at least one slurry loop reactor and the third polymerization zone comprises at least one gas phase reactor.
4. Process for preparing a polymer composition according to claim 1, characterized in that the ethylene-based 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.
5. The process for preparing a polymer composition according to claim 1, wherein said first and second polymerization zones each comprise a slurry loop reactor connected in series, hydrogen is fed to only a first one of these slurry loop reactors, and both said slurry loop reactors are operated under the same/similar conditions or under different conditions.
6. The process for preparing a polymer composition according to claim 1, characterized in that the polymerization of the third ethylene polymer component (C) in the third polymerization zone is carried out in the gas phase in the presence of at least one comonomer different from the comonomer present in the first and/or second polymerization zone.
7. The process for preparing a polymer composition according to claim 1, wherein no hydrogen is fed to the second polymerization zone.
8. The process for preparing a polymer composition according to claim 1, wherein the ethylene polymer component (a) has a lower MFR 2 than the ethylene polymer component (B) and/or the ethylene polymer component (B) has a MFR 2 of from 5 to 50g/10min and/or wherein the ethylene polymer component (C) has a MFR 5 of from 0.01 to 5, both measured according to ISO1133 at 190 ℃ under a load of 2.16kg or 5kg and/or wherein the prepolymer has a MFR 2 in the range of from 5 to 50.
9. The method for producing a polymer composition according to claim 1, wherein the ethylene polymer component (a) has an MFR 2 of 5 to 50g/10 min.
10. The method for producing a polymer composition according to claim 1, wherein the ethylene polymer component (a) has an MFR 2 of 10 to 30g/10 min.
11. The process for preparing a polymer composition according to claim 1, 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 24wt% of ethylene polymer component (a) and/or (B) and/or between 52 and 63wt% of ethylene polymer component (C).
12. The method for producing a polymer composition according to claim 1, 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).
13. The process for preparing a polymer composition according to claim 1, wherein the ethylene polymer components (a) and (B) have a density of 930 to 945kg/m 3 and/or polymer component (C) has a density of 905 to 955kg/m 3.
14. The process for preparing a polymer composition according to claim 1, wherein the density of the multimodal ethylene polymer (a) is from 915 to 955kg/m 3 and/or wherein the MFR2 of the multimodal ethylene polymer (a) is from 0.1 to 10g/10min and/or wherein the multimodal ethylene polymer (a) has an MFR21/MFR2 of from 10 to 40 and/or wherein the multimodal ethylene polymer (a) has an MFR5 of from 1 to 5.
15. The process for preparing a polymer composition according to claim 1, wherein the multimodal ethylene polymer (a) has a density of 930 to 950kg/m 3.
16. The process for preparing a polymer composition according to claim 1, wherein the multimodal ethylene polymer (a) contains gels having a size of 600-1000 micrometers per square meter, the number of gels being 0 to 150 or less and/or the multimodal ethylene polymer (a) has a gel having a size of 300-599 micrometers per square meter, the number of gels being >0 to 1500 or less and/or wherein the multimodal ethylene polymer (a) may have a gel having a size of >1000 micrometers per square meter, the number of gels being 0 to 2 or less and/or the multimodal ethylene polymer (a) may have a gel having a size of 100-299 micrometers per square meter, the number of gels being >0 to 70000 or less.
17. The process for preparing a polymer composition according to claim 1, wherein the multimodal ethylene polymer (a) is prepared using a single site catalyst and/or wherein the ethylene polymer components (a), (B) and (C) of ethylene polymer (a) are prepared using the same single site catalyst and/or each have a MWD of between 2.0 and 5.0.
18. A pipe, a cap, a closure, a rotomoulded article, an artificial grass mat, a geomembrane, a blow moulded article and/or a single or multilayer film comprising the polymer composition prepared using the method according to any one of the preceding claims 1 to 17.
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| EP19186849 | 2019-07-17 | ||
| EP19186849.6 | 2019-07-17 | ||
| PCT/EP2020/069927 WO2021009190A1 (en) | 2019-07-17 | 2020-07-15 | Process for producing a polymer composition |
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| CN116917342A (en) | 2021-03-09 | 2023-10-20 | 博里利斯股份公司 | Polyethylene composition for film layers |
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| WO2023012254A1 (en) | 2021-08-06 | 2023-02-09 | Borealis Ag | Polyethylene copolymer for a film layer |
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| WO2023198612A1 (en) | 2022-04-11 | 2023-10-19 | Borealis Ag | Film |
| WO2023198579A1 (en) | 2022-04-11 | 2023-10-19 | Borealis Ag | Multilayer film |
| WO2023198578A1 (en) | 2022-04-11 | 2023-10-19 | Borealis Ag | Multi-layered article |
| WO2023198600A1 (en) | 2022-04-11 | 2023-10-19 | Borealis Ag | Copolymer |
| EP4265679A1 (en) | 2022-04-21 | 2023-10-25 | Borealis AG | Polymer composition |
| WO2023217750A1 (en) | 2022-05-12 | 2023-11-16 | Borealis Ag | Polyethylene copolymer for a film layer |
| WO2023217751A1 (en) | 2022-05-12 | 2023-11-16 | Borealis Ag | Composition for a film layer |
| EP4275889A1 (en) | 2022-05-12 | 2023-11-15 | Borealis AG | Oriented multilayered film |
| WO2023222658A1 (en) | 2022-05-17 | 2023-11-23 | Borealis Ag | Multilayer polyethylene film |
| EP4296289A1 (en) | 2022-06-23 | 2023-12-27 | Borealis AG | Polyethylene copolymer for a film layer |
| WO2024003206A1 (en) | 2022-07-01 | 2024-01-04 | Borealis Ag | Polyethylene copolymer for a film layer |
| WO2024074320A1 (en) | 2022-10-05 | 2024-04-11 | Borealis Ag | Polyethylene polymer for a film layer |
| WO2024074319A1 (en) | 2022-10-05 | 2024-04-11 | Borealis Ag | Polyethylene composition for a film layer |
| WO2024074318A1 (en) | 2022-10-05 | 2024-04-11 | Borealis Ag | Polyethylene composition for a film layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1764676A (en) * | 2003-03-25 | 2006-04-26 | 博里利斯技术公司 | Metallocene catalyst and preparation of polyolefins therewith |
| EP3257879A1 (en) * | 2016-06-17 | 2017-12-20 | Borealis AG | Bi- or multimodal polyethylene with low unsaturation level |
| CN107835822A (en) * | 2015-07-15 | 2018-03-23 | 道达尔研究技术弗吕公司 | For the technique for preparing polyethylene product |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI86867C (en) | 1990-12-28 | 1992-10-26 | Neste Oy | FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN |
| GB2533770B (en) * | 2014-12-22 | 2021-02-10 | Norner Verdandi As | Polyethylene for pipes |
| EP3887411A1 (en) * | 2018-11-29 | 2021-10-06 | Borealis AG | Polymer composition and process for making the same |
| WO2020109563A1 (en) * | 2018-11-29 | 2020-06-04 | Borealis Ag | Process to produce a polymer and polymer |
-
2020
- 2020-07-15 CN CN202080062123.1A patent/CN114364735B/en active Active
- 2020-07-15 EP EP20737484.4A patent/EP3999566A1/en active Pending
- 2020-07-15 WO PCT/EP2020/069927 patent/WO2021009190A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1764676A (en) * | 2003-03-25 | 2006-04-26 | 博里利斯技术公司 | Metallocene catalyst and preparation of polyolefins therewith |
| CN107835822A (en) * | 2015-07-15 | 2018-03-23 | 道达尔研究技术弗吕公司 | For the technique for preparing polyethylene product |
| EP3257879A1 (en) * | 2016-06-17 | 2017-12-20 | Borealis AG | Bi- or multimodal polyethylene with low unsaturation level |
| 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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