CN114907638B - Polyolefin elastomer/low-branching ultra-high molecular weight polyethylene resin composition and preparation method thereof - Google Patents
Polyolefin elastomer/low-branching ultra-high molecular weight polyethylene resin composition and preparation method thereof Download PDFInfo
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- CN114907638B CN114907638B CN202110172678.8A CN202110172678A CN114907638B CN 114907638 B CN114907638 B CN 114907638B CN 202110172678 A CN202110172678 A CN 202110172678A CN 114907638 B CN114907638 B CN 114907638B
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- polyolefin elastomer
- weight polyethylene
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 76
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 76
- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 75
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000001746 injection moulding Methods 0.000 claims abstract description 36
- 239000002121 nanofiber Substances 0.000 claims abstract description 19
- -1 polypropylene Polymers 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 238000000748 compression moulding Methods 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 238000005187 foaming Methods 0.000 claims abstract description 7
- 230000002787 reinforcement Effects 0.000 claims abstract description 5
- 239000004677 Nylon Substances 0.000 claims abstract description 4
- 229920001778 nylon Polymers 0.000 claims abstract description 4
- 230000035939 shock Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000465 moulding Methods 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000000520 microinjection Methods 0.000 claims description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- NAHBVNMACPIHAH-HLICZWCASA-N p-ii Chemical compound C([C@H]1C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@H](C(N[C@H]2CSSC[C@H](NC(=O)[C@H](CC=3C=CC=CC=3)NC(=O)CNC(=O)[C@H](CCCCN)NC(=O)[C@H](CC=3C=CC(O)=CC=3)NC2=O)C(=O)N[C@@H](CC=2C=CC(O)=CC=2)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CSSC[C@@H](C(=O)N1)NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@@H](N)CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(N)=O)=O)C(C)C)C1=CC=CC=C1 NAHBVNMACPIHAH-HLICZWCASA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 23
- 239000000835 fiber Substances 0.000 description 16
- 229920001971 elastomer Polymers 0.000 description 12
- 238000012545 processing Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76531—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a polyolefin elastomer resin composition and a preparation method thereof. Specifically, the present invention provides a melt-blended resin composition comprising: 80 to 99.9wt% of a polyolefin elastomer and 0.1 to 20wt% of a low branching ultra high molecular weight polyethylene dispersed phase reinforcement (branching degree less than 1/100000C). The low-branching ultra-high molecular weight polyethylene in-situ micro-nano fiber provided by the invention can improve the rigidity and strength of the polyolefin elastomer, and injection molding, compression molding and extrusion molding products manufactured by combining the low-branching ultra-high molecular weight polyethylene in-situ micro-nano fiber with other additives can be applied to the fields of wear resistance, puncture resistance, shock absorption, lightweight foaming, conveyor belts, toughening modification of polypropylene and nylon and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer material modification and processing and forming, and particularly relates to an in-situ forming low-branching ultrahigh-component polyethylene micro-nano fiber reinforced polyolefin elastomer composition and a preparation method thereof.
Background
Polyolefin elastomers (POE) are ethylene/a-olefin copolymers made by high temperature, high pressure solution copolymerization techniques using high temperature (non) metallocene catalysts. By changing the content and type of the comonomer, the distribution of the 'clipping' comonomer in the molecular chain, the molecular weight and the content of the long-chain branch, the aggregation state structure of POE and the corresponding thermal, mechanical and rheological properties thereof can be regulated and controlled. POE is a copolymer chemically bonded by an amorphous soft segment and a crystallizable hard segment. The thermodynamic incompatibility of the different segments results in the formation of heterogeneous aggregate structures. The amorphous soft segment provides elasticity of the rubber at the use temperature, providing mechanical strength with crystals having reversible hot melting and cold curing as physical crosslinking points. At high temperature, the crystals melt to have thermoplasticity, and are processed using processing equipment such as injection molding, extrusion, foaming, and the like of plastics. Compared with the traditional vulcanized rubber, the POE is in a particle form, is easy to blend with other polymers, has low energy consumption for processing and molding, has less pollution, and is nontoxic and recyclable. POE is widely applied to automobile interior and exterior parts, wire and cable jackets, building waterproof coiled materials, biomedical materials, household appliances, photovoltaic packaging, soles, bicycle tires and the like besides automobile tires. However, high molecular weight high melt strength polyolefin elastomers for foaming, thermoforming and blow molding can only be produced by gas phase fluidized bed reactor technology due to the limitations of high temperature (non) metallocene catalysts and high temperature high pressure solution copolymerization technology.
The ultra-high molecular weight polyethylene (UHMWPE) has a molecular weight of 1-9×10 6 g/mol, a high chain entanglement content, self-lubrication, wear resistance, cutting resistance, low temperature impact resistance, environmental stress cracking resistance, fouling resistance, pollution resistance and excellent biocompatibility. Therefore, the high-strength high-modulus UHMWPE fiber manufactured by solution gel spinning is widely used in cut-resistant protective gloves, bulletproof vests, ship ropes and the like, the material manufactured by compression molding and extrusion is applied to artificial joints and special plates by one-time molding or secondary processing, the pipe manufactured by the single screw extrusion method is applied to the wear-resistant and high-temperature-resistant fields, and the UHMWPE microporous membrane manufactured by heat-to-phase separation and unidirectional stretching is applied to lithium battery separators. UHMWPE is used as high-performance engineering plastic, and is also applied to toughening and reinforcing modification of polypropylene and wear-resistant modification of rubber.
The UHMWPE fiber has the characteristics of high strength, high modulus, cutting resistance, corrosion resistance and the like, and is widely applied to reinforced rubber materials. The composite material is manufactured mainly in two modes, wherein the first mode is that chopped UHMWPE fibers are added in the rubber mixing process, so that the abrasion resistance of rubber can be obviously improved (CN 1454928A). However, when the vulcanization or molding temperature is higher than the melting point of the fibers, the fibers melt and the reinforcing effect is reduced. In addition, the chopped fiber has smooth surface, is not easy to adhere with foreign matters, and has low bonding strength between the fiber and a matrix. In addition, the compatibility of the fiber and the matrix is poor, the fiber is difficult to bond with the matrix, and the effect of the fiber reinforced rubber is not obvious. The second is to use an interface modification method to increase the degree of adhesion of the UHMWPE fibers to the fiber matrix. Chinese patent CN 104292510a discloses a method for preparing 1-10 parts of UHMWPE fiber/rubber composite material by interfacial modification technique, although both the tear strength and the peel strength of the fiber of the composite material are improved, the tensile modulus of the composite material is lower. Aizezi M et al (ACS appl. Poly. Mater.2019,1,7,1735-1748) melt blending polyolefin elastomer particles with polypropylene resin to form a bicontinuous phase structure, improving the phase interface between the polyolefin elastomer and polypropylene by radiation crosslinking, and then performing secondary die pressing to orient the polypropylene dispersed phase, wherein the 100% stretching strength and tensile strength of the prepared film are remarkably improved compared with those of the uncrosslinked blend. The rubber composite material with excellent comprehensive performance is prepared by short-cut UHMWPE fiber surface chemical grafting modification at Beijing university Zhang Liqun and the like. In summary, the above processes all require conventional processing of rubber, and the cost of continuous mass production of manufactured articles is high.
In view of the foregoing, there is a lack of a low cost in situ forming low branching ultra high molecular weight polyethylene micro-nanofiber reinforced polyolefin elastomer resin composition suitable for continuous mass production.
Disclosure of Invention
The invention provides a melt blending resin composition which is low in cost and suitable for continuous batch production and in-situ forms low-branching ultra-high molecular weight polyethylene micro-nano fiber reinforced polyolefin elastomer.
In a first aspect of the present invention, there is provided a melt-blended resin composition comprising:
80 to 99.9wt% of a polyolefin elastomer, and
0.1-20Wt% of a low-branching ultra-high molecular weight polyethylene dispersed phase reinforcement, wherein the branching degree of the low-branching ultra-high molecular weight polyethylene is less than 1/100000 ℃.
In another preferred example, the powder morphology of the low-branching ultra-high molecular weight polyethylene is irregular or spheroid-like particles, and the low-branching ultra-high molecular weight polyethylene consists of secondary spheroid-like particles connected by nanofibers.
In another preferred embodiment, the low branched ultra high molecular weight polyethylene further has one or more characteristics selected from the group consisting of:
The viscosity average molecular weight is 1.0-9 multiplied by 10 6 g/mol;
The particle size is 40-300 μm;
the melting point of the powder is 140-145 ℃;
The crystallinity is 65-80wt%.
In another preferred embodiment, the low branched ultra high molecular weight polyethylene micro-nanofibers formed in situ in the composition have a thickness of 50nm to 1um.
In another preferred embodiment, the size of the irregular particles of the low branched ultra high molecular weight polyethylene in the composition is 100nm to 50um.
In another preferred embodiment, the polyolefin elastomer is an ethylene/a-olefin copolymer containing up to 50wt% of a-olefin.
In another preferred embodiment, the polyolefin elastomer is selected from the group consisting of: engage TM series of Dow, mitsui Chemical Tafmer TM series, exxonMobile VistaMaxx TM series, LG Lucene TM series, SABIC Fortify TM series, or combinations thereof.
In another preferred embodiment, the polyolefin elastomer is one wherein the a-olefin is selected from the group consisting of: propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, or combinations thereof; preferably, the a-olefin is selected from the group consisting of: 1-butene, 1-octene, or a combination thereof.
In another preferred embodiment, the polyolefin elastomer has a molecular weight of 50 to 300kg/mol and a molecular weight distribution of 1.5 to 3, and a portion of the polyolefin elastomer contains long chain branches.
In another preferred embodiment, the polyolefin elastomer has a melt flow index of 0.2 to 30g/10min (2.16 kg @190 ℃) and a density of 0.85 to 0.90g/cm 3 and a comonomer content of less than or equal to 50wt%.
In another preferred embodiment, the polyolefin elastomer has a melting point of 30-120℃and a glass transition temperature of-60-30 ℃.
In a second aspect of the present invention, there is provided a method for producing the resin composition according to the first aspect of the present invention, the method comprising the steps of:
optionally (1) premixing: uniformly mixing polyolefin elastomer particles and low-branching ultra-high molecular weight polyethylene powder;
(2) Melt blending: melt blending the polyolefin elastomer particles and the low-branching ultra-high molecular weight polyethylene powder in a melt blending device, wherein the blending is performed at a temperature above the melting point of the polyolefin elastomer and below the decomposition temperature of the polyethylene, and the rotational speed of the melt blending device is 50-500rpm; preferably, the resin composition is pelletized after the completion of blending.
In another preferred embodiment, the premixing step is performed using a high speed mixer or other mixing device.
In another preferred embodiment, the melt blending apparatus is selected from the group consisting of: reverse twin-screw extruder, in-phase twin-screw extruder, single-screw extruder.
In another preferred embodiment, the temperature of the blending is 80-250 ℃.
In another preferred embodiment, the melt blending apparatus is operated at a speed of 200 to 500rpm.
In a third aspect of the present invention, there is provided an article prepared from or containing a resin composition according to the first aspect of the present invention.
In a fourth aspect, the present invention provides a method of preparing an article according to the third aspect of the present invention, the article being shaped by a method selected from the group (i), (ii) or (iii):
(i) Injection molding: injection molding the resin composition according to the first aspect of the present invention using a micro injection molding machine or an injection molding machine; wherein the injection molding is carried out at the temperature of 100-250 ℃, and the temperature of the mold is 0-80 ℃ in the injection molding process;
(ii) Compression molding: molding the resin composition according to the first aspect of the present invention at a molding temperature of at least the melting point of the polyolefin elastomer and at most 190 ℃;
(iii) Extrusion molding: extrusion molding the resin composition according to the first aspect of the present invention at 120-250 ℃; and in the extrusion molding process, the temperature of the die is the melting point of the polyolefin elastomer to 220 ℃.
In another preferred embodiment, the ultra-high molecular weight polyethylene in injection molded, compression molded and extrusion molded articles exhibits micro-nanofiber and spheroid micro-nano particles.
In another preferred embodiment, the tensile modulus of the resin composition is increased by a factor of 2 to 40 when compared to the neat polyolefin elastomer when using an injection molding process.
In another preferred embodiment, when an injection molding process is employed, the 100% elongation strength of the resin composition is increased by a factor of 1 to 5 compared to the pure polyolefin elastomer.
In another preferred embodiment, when the compression molding process is employed, the tensile modulus of the resin composition is increased by a factor of 2 to 35 compared to the neat polyolefin elastomer.
In another preferred embodiment, when the compression molding process is employed, the 100% elongation strength of the resin composition is improved by 1 to 4 times as compared to the pure polyolefin elastomer.
In another preferred embodiment, the article is used to prepare a rubber and plastic article selected from the group consisting of: wear-resistant soles, puncture-resistant films, shock absorbers, foaming materials, conveyor belts, and toughening modification of polypropylene or nylon.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Drawings
FIG. 1 is a topography of a low branching ultra high molecular weight polyethylene powder used in the present invention;
FIG. 2 is a tensile stress-strain curve of the microinjection and molding composite of examples 2.1-3 and 3.1-3.4 of the present invention;
FIG. 3 is a topography of low branching ultra high molecular weight polyethylene micro-nanofibers in injection and compression molded sheets of examples 2.1,3.2 and 3.4 of this invention.
Detailed Description
The present inventors have made intensive studies for a long time to develop a resin composition comprising a polyolefin elastomer and a low-branched ultra-high molecular weight polyethylene dispersed phase reinforcement. By adjusting the content of the low-branching ultra-high molecular weight polyethylene dispersed phase reinforcing body, the melt blending resin composition with improved rigidity and strength is prepared. Based on the above findings, the inventors have completed the present invention.
Preparation of resin composition
In order to overcome the defects of the traditional ultra-high molecular weight polyethylene chopped fiber reinforced rubber composite material and the processing method thereof, the invention provides an in-situ forming low-branching ultra-high molecular weight polyethylene micro-nano fiber reinforced polyolefin elastomer composition and a preparation method thereof, wherein the method comprises the following steps:
(1) Premixing: the proportionally weighed polyolefin elastomer particles and ultra-high molecular weight polyethylene powder are mixed uniformly using a high speed mixer or other mixing device. The premixing process section can also be omitted by feeding in batches through a twin-screw extruder.
(2) Melt blending: melt blending by using a double-screw extruder, wherein the blending temperature is 100-250 ℃, the rotating speed is 100-500rpm, and granulating.
(3) And (3) forming: the forming is carried out by adopting any one of the following methods:
Injection molding: the micro injection molding machine or injection molding machine is used, the injection molding temperature is 100-250 ℃, the mold temperature is 0-80 ℃, and the tensile modulus and 100% stretching strength of the composition are respectively improved by 40 times and 5 times compared with the pure polyolefin elastomer.
Compression molding: compression molding is carried out at a compression molding temperature of more than the melting point of the polyolefin elastomer and less than 190 ℃, and the tensile modulus and 100% stretching strength of the composition are respectively improved by 35 times and 4 times compared with the pure polyolefin elastomer.
The ultra-high molecular weight polyethylene powder in step 1 is random or spheroid loose porous powder, contains spheroid secondary particles (figure 1) connected by nanofiber, has branching degree less than 1/100000C, viscosity average molecular weight of 1.5-9×10 6 g/mol, particle size of 40-300um, melting point of 140-145 deg.C, and crystallinity of 65-80wt%.
The polyolefin elastomer particles described in step 1 are ethylene/a-olefin copolymers containing at most 50wt% of a-olefin, the a-olefin being selected from propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like, preferably from ethylene/1-butene copolymers and ethylene/1-octene copolymers, having a melt flow index of from 0.2 to 30g/10min (2.16 kg@190 ℃), a weight average molecular weight of from 50 to 300kg/mol, a molecular weight distribution of from 1.5 to 3, a density of from 0.85 to 0.92g/cm 3, a melting point of from 30 to 120 ℃, and a glass transition temperature of from-60 to 30 ℃. The polyolefin elastomer product may be selected from the Dow company Engage TM series, mitsui Chemical company Tafmer TM series, exxonMobile company VistaMaxx TM series, LG company Lucene TM series, SABIC company Fortify TM series, and combinations thereof.
The processes described in steps 2 and 3 may be carried out in a twin screw extruder, preferably the twin screw extruder may be a reverse twin screw extruder, an in-phase twin screw extruder, or a single screw extruder.
The composition prepared by the step 2 is blended with other additives and then molded to prepare related products, such as wear-resistant soles, puncture-resistant films, shock absorbers, foaming materials, conveyor belts and the like, and can also be applied to toughening modification of polypropylene and nylon.
Low branching ultra high molecular weight polyethylene as reinforcement
In the present invention, the low branched ultra high molecular weight polyethylene used may be prepared by methods known in the art, and in a preferred embodiment, by the following methods:
The heterogeneous catalytic system which is formed by taking a catalyst and an alkyl aluminum compound as cocatalysts is contacted with ethylene and reacts for 1-18 hours under the condition that the partial pressure of the ethylene is 0.2-10 Mpa and 0-100 ℃. The molar ratio of catalyst to cocatalyst is 1:1-5000, and can be polymerized for 2-6 hours at 1:10-2000, so as to maintain the catalytic activity, polymer property and production cost in a good range, preferably 1:20-500.
Wherein the catalyst may be the corresponding catalyst known in the art, but in a preferred embodiment the catalyst is prepared by steps (a) - (d), and optionally step (e):
(a) Under the protection of inert gas, anhydrous magnesium chloride is added into an inert hydrocarbon solvent, C1-C10 alcohol with the weight of magnesium chloride being more than or equal to 2 equivalent is added under the stirring condition for contact, the system is kept at 60-120 ℃ to form a uniform solution, then the temperature is reduced to below-30 ℃, and the stirring rotating speed and the rotating speed of a hypergravity reactor are controlled to obtain precursor slurry P-I; wherein the cooling speed is preferably 1-10 ℃/min; the inert gas is preferably nitrogen; preferably 2 to 6 equivalents of C1-C10 alcohol; more preferably 2-4 equivalents;
(b) Contacting the precursor slurry I obtained in the step (a) with aluminum alkyl at a temperature lower than-30 ℃ for 1-2h, and then maintaining at 60-120 ℃ for 2-6h to obtain precursor slurry P-II;
(c) The precursor slurry II obtained in the step (b) is contacted with a hydrocarbon solution of a titanium compound for 0.5 to 1 hour at the temperature below minus 30 ℃ and then is heated and kept for 2 to 6 hours at the temperature of 60 to 120 ℃ to obtain catalyst slurry C-III; the heating rate is preferably 1-10 ℃/min;
(d) Filtering the catalyst slurry C-III obtained in the step (C);
(e) Drying the catalyst slurry obtained in step (d);
Wherein the titanium compound is soluble in hydrocarbon solvents such as TiCl 4 or Ti (R) 4, wherein R is C1-C6 alkyl, allyl, benzyl or NMe 2, or other titanium compounds soluble in hydrocarbon solvents.
The molar ratio of titanium complex to magnesium chloride may be from 0.3 to 0.8:1, preferably from 0.4 to 0.6:1, most preferably 0.5:1; in the process of the complexation titanium-carrying reaction of the alkyl complex of the fourth subgroup metal titanium, the temperature rising speed of the reaction needs to be controlled, and the temperature rising speed is 1-10 ℃/min, preferably 1-5 ℃/min, and most preferably 1 ℃/min; the temperature of the final titanium-carrying contact reaction is controlled at 60-120 ℃, preferably 80-100 ℃, and the reaction time is controlled at 2-6h, preferably 4-5h at the preferred temperature.
The polymerization is generally carried out in inert organic solvents, for example hydrocarbons, cyclic hydrocarbons or aromatic hydrocarbons, but also in halogenated solvents, such as dichloroethane, chlorobenzene, it being possible for the inert organic solvents to be used with hydrocarbons of less than 12 carbons in order to facilitate the operation of the reactor. Examples are, but are not limited to, propane, isobutane, n-pentane, 2-methylbutane, n-hexane, cyclohexane, toluene, chlorobenzene, dichloroethane, and mixtures thereof.
The polymerization temperature is maintained at 0 to 100℃and may be maintained at 40 to 80℃for good catalytic activity and productivity.
Better reactor operating parameters and polymers can be obtained by operating at a partial pressure of 0.2 to 1.5Mpa for polymerized ethylene or 0.2 to 1.5Mpa for polymerized ethylene/0.01-0.1 Mpa for hydrogen.
The cocatalyst is an alkylaluminum compound, alkylaluminoxane or a weakly coordinating anion; the alkyl aluminum compound is preferably AlEt 3,AlMe3 or Al (i-Bu) 3,AlEt2 Cl, and the alkyl aluminoxane is preferably methylaluminoxane, MMAO (modified methylaluminoxane) or the like; the weakly coordinating anion is preferably [B(3,5-(CF3)2C6H3)4]-、-OSO2CF3 or ((3, 5- (CF 3)2)C6H3)4B-) catalyst and cocatalyst may be added to the system in any order to allow the polymerization, preferably AlEt 3. The ratio of catalyst to cocatalyst used for the polymerization may vary, typically for a period of time ranging from 1 to 18 hours, the molar ratio of catalyst to cocatalyst ranging from 1:1 to 5000, typically from 1:10 to 2000 for 2 to 6 hours, in order to maintain the catalytic activity, polymer properties and production costs in the preferred ranges, preferably from 1:20 to 500.
In the preferred embodiment of the invention, the catalyst catalyzes ethylene polymerization at 40-80 ℃ and ethylene pressure of 0.2-0.8MPa to obtain ultra-high molecular weight polyethylene particles, wherein the polymerization activity is higher than 100Kg PE/g Cat, at least 95% of the powder obtained by polymerization passes through a 150-micron mesh sieve, the medium diameter (d 50) measured by a laser diffraction scattering method is 50 μm- 50 -80 μm, more preferably 50 μm- 50 -70 μm, and the viscosity average molecular weight of the polyethylene is 150-1000 ten thousand; more preferably, the viscosity average molecular weight of the polyethylene is 150-800 ten thousand. The branched structure was analyzed by melt 13 C NMR and it was confirmed that the polymer contained less than 1 branch per 100,000 backbone carbon atoms.
Compared with the prior art, the invention has the main advantages that:
1. The invention uses a common double-screw extruder to directly melt blend the polyolefin elastomer and the low-branching ultra-high molecular weight polyethylene powder to form an ultra-high molecular weight polyethylene micro-nano fiber structure in situ, and maintains the micro-nano fiber structure and generates orientation by adjusting injection molding and mould pressing processes, thereby greatly improving the tensile modulus and the stretching strength of the polyolefin elastomer, and further simultaneously improving the rigidity and the strength of rubber.
2. The low-branching ultra-high molecular weight polyethylene reinforced polyolefin elastomer composition provided by the invention can be manufactured in common plastic processing equipment, has universality and low processing cost, and does not need surface treatment on ultra-high molecular weight polyethylene micro-nano fibers.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Detailed Description
Specific examples are provided to illustrate the superiority of the novel low branching ultra high molecular weight polyethylene in situ micro-nanofiber reinforced polyolefin elastomer compositions and methods of preparation of the present invention and the controllability of the properties of the articles. The scope of the invention is not limited to the process operating conditions and article properties and applications in the examples.
Universal test method
Powder morphology and morphology test in composition: after HITACHI MCI000,000 vacuum platings, characterizing the powder morphology and the low temperature brittle fracture morphology of the composition using a HITACHI Regulus 8100 scanning electron microscope at 10KV and 10 uA;
melting point and crystallinity test of the powder: DSC2000 was used, provided that 3-8mg of the powder pieces were placed in an aluminum dry pan, heated to 160℃at a heating rate of 10℃per minute under a nitrogen atmosphere, kept at a constant temperature for 3 minutes, and then cooled to 40℃at a cooling rate of 10℃per minute, and kept at a constant temperature for 3 minutes. The temperature was raised to 160℃at a heating rate of 10℃per minute. Crystallinity is 100%/290 (KJ/mol) of melting enthalpy.
Mechanical property test: injection molded samples injection molded ISO20573-TypeCP multipurpose spline was prepared as per the examples. The molded sheet was cut into ISO20573-TypeCP multipurpose bars using a die cutter. The test is carried out in a WDW-20 electronic universal tester, the stretching rate is 50mm/min, the environment temperature is 23 ℃, and the average value of 5-6 samples is obtained by mechanical property data.
Compound viscosity test: the low temperature molded samples were cut into 25mm diameter disks and the composite viscosity in the range of 0.01-100rad/s was measured in a TA Instrument ARES-G2 rotary rheometer at 160 ℃.
The twin screw extruder and microinjection molding used in the present invention were HAAKE PolyLab OS RheoDrive twin screw extruder (L/D40) and HAAKE MiniJet II injection molding machine from Thermo Scientific company. The molding press is an XH-406 universal tablet press manufactured by Xinhua precision detection instrument company, and is provided with two layers of independent heating and pressurizing units, the molding is performed in a lower layer unit, and the cooling crystallization is performed on an upper layer. The mechanical property test uses ISO20573-TypeCP multipurpose spline.
The raw material used in the invention is low-branching ultra-high molecular weight polyethylene, the pilot-scale product is UH, the viscosity average molecular weight is 3.89 multiplied by 10 6 g/mol, the melting point is 142.5 ℃, the crystallinity is 81.7%, the branching degree is less than 1/100000, and the powder form is shown in figure 1. The low branched ultra high molecular weight polyethylene may be prepared by any suitable method known in the art, such as the low branched ultra high molecular weight polyethylene described in chinese patent 201010554473.8.
In a preferred embodiment, the low branching ultra high molecular weight polyethylene is prepared by the following process:
The 30L stainless steel stirring polymerization kettle is replaced by N 2, 8kg of hexane is used for adding AlEt 3 (10 mL) into the kettle under the condition of 0.4MPa nitrogen, the stirring rotation speed is controlled to be 250rpm, the temperature in the kettle is preheated to about 60 ℃, then 30mg Cat is flushed into the polymerization kettle by using 2kg of hexane under the condition of 0.4MPa nitrogen pressure, the activation is carried out for 10min, then the nitrogen pressure in the kettle is removed, ethylene gas is introduced again, the pressure in the kettle is enabled to reach 0.4MPa, the temperature in the kettle is controlled to be 70 ℃, the ethylene is stopped to be introduced after polymerization is carried out for 2h, the temperature in the kettle is reduced to be below 50 ℃ by using a circulating constant-temperature oil bath, the gas in the system is discharged, and the granular polymer is obtained after drying. Wherein the catalyst is prepared by the following method:
(a) Under the protection of inert gas, anhydrous magnesium chloride is added into an inert hydrocarbon solvent, C1-C10 alcohol with the weight of magnesium chloride being more than or equal to 2 equivalent is added under the stirring condition for contact, the system is kept at 60-120 ℃ to form a uniform solution, then the temperature is reduced to below-30 ℃, and the stirring rotating speed and the rotating speed of a hypergravity reactor are controlled to obtain precursor slurry P-I; the cooling speed is 1-10 ℃/min;
(b) Contacting the precursor slurry I obtained in the step (a) with aluminum alkyl at a temperature lower than-30 ℃ for 1-2h, and then maintaining at 60-120 ℃ for 2-6h to obtain precursor slurry P-II;
(c) The precursor slurry II obtained in the step (b) is contacted with a hydrocarbon solution of a titanium compound for 0.5 to 1 hour at the temperature below minus 30 ℃ and then is heated and kept for 2 to 6 hours at the temperature of 60 to 120 ℃ to obtain catalyst slurry C-III; the heating rate is preferably 1-10 ℃/min;
(d) Filtering the catalyst slurry C-III obtained in the step (C);
(e) Drying the catalyst slurry obtained in the step (d) to obtain the catalyst.
The polyolefin elastomer particles used in the invention are Engage TM products of the Dow chemical company, the molecular weight is 71.7kg/mol, the molecular weight distribution is 2.27, the branching degree is 35.1CH 3/1000C, the 1-octene content is 8.7mol percent, and the melting point is 78 ℃.
Example 1.1 blending example E1
Weighing 800g of polyolefin elastomer, 200g of ultra-high molecular weight polyethylene powder and 5g of antioxidant (1010), uniformly premixing, pouring into a feeding port of a double-screw extruder, blending at 190-200-210-220-220-240-220-220-210-200 ℃, rotating at 200rpm, torque at 74Nm, feeding at 15%, cooling in a water bath after extrusion, granulating, and vacuum drying at 60 ℃ for 24 hours. Under the same condition, blending, granulating and drying.
Example 1.2 blending example E2
Weighing 800g of polyolefin elastomer, 200g of ultra-high molecular weight polyethylene powder and 5g of antioxidant (1010), uniformly premixing, pouring into a feeding port of a double-screw extruder, blending at 110-120-130-130-130-135-130-130-125-120 ℃, rotating at 100rpm, torque of 90-100Nm, feeding at a feeding rate of 6%, cooling in a water bath after extrusion, granulating, and vacuum drying at 60 ℃ for 24 hours. Under the same condition, blending, granulating and drying.
Example 1.3 blending example E3
Weighing 800g of polyolefin elastomer, 200g of ultra-high molecular weight polyethylene powder and 5g of antioxidant (1010), uniformly premixing, pouring into a feeding port of a double-screw extruder, blending at 140-150-150-160-160-170-160-160-160-150 ℃, rotating at 100rpm, torque of 90-100Nm, feeding at 10% of feeding rate, cooling in a water bath after extrusion, granulating, and vacuum drying at 60 ℃ for 24 hours. Under the same condition, blending, granulating and drying.
Example 1.4 blending example E4
900G of polyolefin elastomer, 100g of ultra-high molecular weight polyethylene powder and 5g of antioxidant (1010) are weighed, evenly premixed, poured into a feeding port of a double-screw extruder, the blending temperature is 110-120-130-130-140-145-140-140-135-130 ℃, the rotating speed is 100rpm, the torque is 95Nm, the feeding rate is 8%, cooled in a water bath after extrusion, granulated and dried in vacuum at 60 ℃ for 24 hours. Under the same condition, blending, granulating and drying.
Example 1.5 blending example E5
900G of polyolefin elastomer, 100g of ultra-high molecular weight polyethylene powder and 5g of antioxidant (1010) are weighed, evenly premixed and poured into a feeding port of a double-screw extruder. The temperature from the feeding section of the extruder to the die opening is 110-120-130-130-130-135-130-130-125-120 ℃, the rotating speed is 100rpm, the torque is 80-100Nm, the feeding speed is 6-8%, the water bath is cooled after extrusion, the pelletization is carried out, and the vacuum drying is carried out for 24 hours at 60 ℃.
Comparative example 1.1 blend comparative example E6
1000G of polyolefin elastomer and 5g of antioxidant (1010) are weighed, evenly premixed, poured into a feeding port of a double-screw extruder, extruded at the temperature of 140-150-160-170-180-190-190-180-180-170 ℃, at the rotating speed of 150rpm, torque of 75Nm and feeding speed of 15%, cooled in a water bath after extrusion, granulated and dried in vacuum at the temperature of 60 ℃ for 24 hours. Under the same condition, blending, granulating and drying.
EXAMPLE 2.1 injection moulding example IM1
Injection molding was performed in Thermo SCIENTIFIC HAAKE MiniJet II using the E1 pelleting composition to prepare ISO20573-TypeCP multipurpose spline at 220℃injection molding temperature, 90MPa injection molding pressure, 30s injection molding time, 60MPa dwell pressure, 1min dwell time, 40℃mold temperature, and 5min crystallization time.
EXAMPLE 2.2 injection moulding example IM2
Injection molding was performed in Thermo SCIENTIFIC HAAKE MiniJet II using the E4 pelletized composition to prepare ISO20573-TypeCP multipurpose spline at 125℃injection molding temperature, 90MPa injection molding pressure, 30s injection molding time, 60MPa dwell pressure, 1min dwell time, 40℃mold temperature, and 5min crystallization time.
EXAMPLE 2.3 injection moulding example IM3
Injection molding was performed in Thermo SCIENTIFIC HAAKE MiniJet II using the E2 pelleting composition to prepare ISO20573-TypeCP multipurpose spline at 135℃injection pressure 90MPa injection time 30s, 60MPa dwell pressure 1min, mold temperature 40℃crystallization time 5min.
Comparative example 2.1 injection moulding comparative example IM4
The E6 pelletized polyolefin elastomer is used for injection molding in a Thermo SCIENTIFIC HAAKE MiniJet II to prepare ISO20573-TypeCP multipurpose spline, the injection molding temperature is 160 ℃, the injection molding pressure is 90MPa, the injection molding time is 30s, the holding pressure is 60MPa, the holding time is 1min, the mold temperature is 40 ℃, and the crystallization time is 5min.
Example 3.1 molding examples CM1-3
The E2 pelleting composition was pre-pressed for 10min at 125, 135 and 142 ℃ and the same 2.5MPa, pressed for 5min at 10MPa, and cooled and crystallized for 5-10min at 40-60 ℃ to prepare a sheet with a thickness of 2 mm. Standard bars 5-6 were prepared using a die cutter and ISO20573-TypeCP cut-off knife.
Example 3.2 molding examples CM4-6
The composition granulated using E3 was pre-pressed in a molding machine at 120, 125, 135℃and the same 2.5MPa for 10min, pressed at 10MPa for 5min and cooled and crystallized at 40-60℃for 5-10min to prepare a sheet having a thickness of 2mm and a composite viscosity of 13.5kPa. S at 10rad/s and 120 ℃. Standard bars 5-6 were prepared using a die cutter and ISO20573-TypeCP cut-off knife.
EXAMPLE 3.3 molding example CM7
The composition granulated by E1 was pre-pressed in a molding machine at 120℃and 2.5MPa for 10min, pressed at 10MPa for 5min and cooled and crystallized at 60℃for 5-10min to prepare a sheet having a thickness of 2 mm. Standard bars 5-6 were prepared using a die cutter and ISO20573-TypeCP cut-off knife.
Examples 3.4 molding examples CM8-9
Prepressing the composition granulated by E4 and E5 in a molding machine for 10min at 123 ℃ and 2.5MPa, pressing for 5min at 10MPa, and cooling and crystallizing for 5-10min at 40-60 ℃ to prepare a sheet with the thickness of 2 mm. The complex viscosity at 10rad/s and 120℃is 7.42kPa. Standard bars 5-6 were prepared using a die cutter and ISO20573-TypeCP cut-off knife.
Comparative example 3.1 compression molding comparative example CM10
The polyolefin elastomer pelletized using E6 was pre-pressed in a molding machine at 125℃and 2.5MPa for 10 minutes, then pressed at 10MPa for 5 minutes, and cooled and crystallized at 40℃for 10 minutes to prepare a sheet having a thickness of 2mm and a composite viscosity of 4.54kPa. S at 10rad/s and 120 ℃. Standard bars 5-6 were prepared using a die cutter and ISO20573-TypeCP cut-off knife.
The test results of the samples prepared in the above respective examples are shown in table 1 below:
TABLE 1
The results of the above blending examples 1.1-6 and microinjection examples 2.1-3 show that when polyolefin elastomers are blended with low branched high molecular weight polyethylene at high temperature, the twin screw torque is not great (example 1.1), whereas when blending is carried out at low temperature according to the in situ micro-nano-fiberization technique, the torque is great (examples 1.2 and 1.5), the rotational speed of the extruder needs to be reduced in order to reduce the melt viscosity of the composition and the heat generation of extrusion friction, which results in reduced production efficiency, is not suitable for mass production, and more importantly, the rotational speed of the extruder is reduced to reduce the shear rate, which deteriorates the dispersibility of the ultra-high molecular weight polyethylene powder. It is interesting, however, that the composite retains a hard elasticity at low temperature injection molding of such low temperature blended particles, and does not exhibit a pronounced yield behavior (examples 2.3-IM3 and the curves of fig. 2-IM 3). When the ultra-high molecular weight polyethylene is blended above the melting point and injection molded at low temperature, only 10wt percent of the ultra-high molecular weight polyethylene is needed to be added, so that the performance of the composite material can be greatly improved (example 2.2 and the attached drawing 2-IM 2). Thus, polyolefin elastomers when blended with low branching ultra high molecular weight polyethylene and processed require a balance of processability and article properties.
As shown in table 1, when the forming temperature (die temperature) was reduced to a temperature near the melting point of the ultra-high molecular weight polyethylene (125-145 ℃), the chain relaxation rate was reduced, contributing to the orientation and retention of the micro-nanofibers (fig. 3), thereby significantly enhancing the performance of the composite:
(1) Microinjection molding examples 2.1-2.3 the results (Table 1) show that when the low branched ultra high molecular weight polyethylene content in the polyolefin elastomer matrix exceeds 10wt%, the injection molded composite skin readily forms a physical network of three-dimensional chain entanglement, the micronanofibers orient (FIG. 3, POE20 UH-IM), and the composite exhibits yield behavior even at high temperature injection molding (examples 2.1-3 and FIG. 2-IM). Thus, the low branching ultra high molecular weight polyethylene should be present in an amount of less than 20wt%, more preferably less than 10wt%, while simultaneously compromising processability and the elastic properties as well as abrasion resistance properties of the composite.
(2) The results of compression molding examples 3.1-3.4 (Table 1) show that the low branched ultra high molecular weight polyethylene retains the nanofiber structure (FIG. 3, POE10UH-CM and POEUH-CM) at compression molding temperatures above the melting point of the polyolefin elastomer and near the melting point of the low branched ultra high molecular weight polyethylene powder, significantly enhancing the mechanical properties in the composite and the composite retains the hard elastomer properties; with the increase of the content of the ultra-high molecular weight polyethylene and the increase of the molding temperature, the tensile strength of the composite material is not greatly changed, but the tensile modulus and the elongation at break are increased, which indicates that the increase of the molding temperature is beneficial to the adhesion among particles. When the low branched ultra high molecular weight polyethylene content in the polyolefin elastomer matrix exceeds 20wt%, the mechanical properties of the molded composite are greatly increased, but the three-dimensional chain entanglement network greatly increases the composite viscosity of the composition, affecting the melt flow properties thereof. Therefore, the processing performance, the elastic performance of the composite material, the wear resistance and the like are combined, and the content of the low-branching ultra-high molecular weight polyethylene is less than 20 weight percent. The rheological property of the molding material is tested by using an ARES-G2 rheometer, and the compound viscosity of POE20UH, POE10UH and POE at 0.1rad/s are 49, 9.3 and 4.8kP.s respectively, which shows that the addition of ultra-high molecular weight polyethylene greatly increases the melt viscosity of the polyolefin elastomer, so that the composition has potential application value in the fields of repeatedly processing high-melt-strength elastomer and foaming materials thereof.
When the composition is applied to industrial production, the blending and processing forming process is optimized, and the dosage of the low-branching ultra-high molecular weight polyethylene can be obviously reduced, so that the production cost is reduced. According to the performance requirements (elastic performance, rigidity and wear resistance special performance) of the composite material, the composite resin containing the ultra-high molecular weight polyethylene with different components can be selected to meet the requirements of production and products.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (20)
1. A melt blended resin composition comprising:
80 to 99.9wt% of a polyolefin elastomer, and
0.1-20Wt% of a low-branching ultra-high molecular weight polyethylene dispersed phase reinforcement, wherein the branching degree of the low-branching ultra-high molecular weight polyethylene is less than 1/100000C;
wherein the polyolefin elastomer is an ethylene/a-olefin copolymer containing at most 50wt% of a-olefin; and the melt-blended resin composition is prepared by the steps of:
optionally (1) premixing: uniformly mixing polyolefin elastomer particles and low-branching ultra-high molecular weight polyethylene powder;
(2) Melt blending: melt blending the polyolefin elastomer particles and the low-branching ultra-high molecular weight polyethylene powder in a melt blending device, wherein the blending is performed at a temperature above the melting point of the polyolefin elastomer and below the decomposition temperature of the polyethylene, and the rotational speed of the melt blending device is 50-500rpm;
The powder morphology of the low-branching ultra-high molecular weight polyethylene is irregular or spheroid particles, and the low-branching ultra-high molecular weight polyethylene consists of secondary spheroid particles connected by nano fibers;
The thickness of the low-branching ultra-high molecular weight polyethylene micro-nano fiber formed in situ in the composition is 50nm-1um.
2. The resin composition of claim 1, wherein the polyolefin elastomer has a melt flow index of 0.2 to 30g/10min, a density of 0.85 to 0.90g/cm 3, and a comonomer content of 50 wt.% or less, measured at 2.16kg @190 ℃.
3. The resin composition of claim 1, wherein the polyolefin elastomer is selected from the group consisting of: engage TM series of Dow, mitsui chemical Tafmer TM series, exxonMobile VistaMaxx TM series, LG Lucene TM series, SABIC Fortify TM series, or combinations thereof.
4. A melt blended resin composition according to any one of claims 1-3, wherein said low branched ultra high molecular weight polyethylene further has one or more characteristics selected from the group consisting of:
The viscosity average molecular weight is 1.0X10 6-9×106 g/mol;
The particle size is 40-300 μm;
the melting point of the powder is 140-145 ℃.
5. The resin composition of claim 1 wherein said polyolefin elastomer is selected from the group consisting of: propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, or combinations thereof.
6. The resin composition of claim 1, wherein the a-olefin is selected from the group consisting of: 1-butene, 1-hexene, 1-octene.
7. The resin composition of claim 1, wherein the low branched ultra high molecular weight polyethylene is prepared by:
The heterogeneous catalytic system which is formed by taking a catalyst and an alkyl aluminum compound as cocatalysts is contacted with ethylene and reacts for 1-18 hours under the condition that the partial pressure of the ethylene is 0.2-10 Mpa and 0-100 ℃.
8. The resin composition of claim 7, wherein the catalyst is prepared by steps (a) - (d), and optionally step (e):
(a) Under the protection of inert gas, anhydrous magnesium chloride is added into an inert hydrocarbon solvent, C1-C10 alcohol with the weight of magnesium chloride being more than or equal to 2 equivalent is added under the stirring condition for contact, the system is kept at 60-120 ℃ to form a uniform solution, then the temperature is reduced to below-30 ℃, and the stirring rotating speed and the rotating speed of a hypergravity reactor are controlled to obtain precursor slurry P-I;
(b) Contacting the precursor slurry I obtained in the step (a) with aluminum alkyl at a temperature lower than-30 ℃ for 1-2h, and then maintaining at 60-120 ℃ for 2-6h to obtain precursor slurry P-II;
(c) The precursor slurry II obtained in the step (b) is contacted with a hydrocarbon solution of a titanium compound for 0.5 to 1 hour at the temperature below minus 30 ℃ and then is heated and kept for 2 to 6 hours at the temperature of 60 to 120 ℃ to obtain catalyst slurry C-III;
(d) Filtering the catalyst slurry C-III obtained in the step (C);
(e) Drying the catalyst slurry obtained in step (d).
9. The resin composition according to claim 8, wherein in the step (a), the cooling rate is preferably 1 to 10 ℃/min.
10. The resin composition of claim 8, wherein the titanium compound is selected from the group consisting of: tiCl 4 or Ti (R) 4, where R is C1-C6 alkyl, allyl, benzyl or NMe 2.
11. The resin composition of claim 8, wherein in step (a), the inert gas is nitrogen.
12. The resin composition of claim 8, wherein in the step (a), the amount of the C1-C10 alcohol added is 2 to 6 equivalents.
13. The resin composition of claim 8, wherein in step (a), the amount of the C1-C10 alcohol added is 2 to 4 equivalents.
14. The resin composition according to claim 8, wherein in the step (c), the temperature rising rate is 1 to 10 ℃/min.
15. The method for producing a resin composition according to claim 1, comprising the steps of:
optionally (1) premixing: uniformly mixing polyolefin elastomer particles and low-branching ultra-high molecular weight polyethylene powder;
(2) Melt blending: and melt blending the polyolefin elastomer particles and the low-branching ultra-high molecular weight polyethylene powder in a melt blending device, wherein the blending is performed at a temperature above the melting point of the polyolefin elastomer and below the decomposition temperature of the polyethylene, and the rotating speed of the melt blending device is 50-500rpm.
16. The method of claim 15 wherein the resin composition is pelletized after blending is complete.
17. The method of claim 15, wherein the blending is at a temperature of 80 ℃ to 250 ℃.
18. An article prepared from the resin composition of any one of claims 1-14 or comprising the resin composition of any one of claims 1-14.
19. The method of making an article according to claim 18, wherein the article is shaped by a method selected from the group consisting of (i), (ii) and (iii):
(i) Injection molding: injection molding the resin composition according to any one of claims 1 to 14 using a micro-injection molding machine or an injection molding machine; wherein the injection molding is carried out at the temperature of 100-250 ℃, and the temperature of the mold is 0-80 ℃ in the injection molding process;
(ii) Compression molding: molding the resin composition according to any one of claims 1 to 14 at a molding temperature of at least the melting point of the polyolefin elastomer and at most 190 ℃;
(iii) Extrusion molding: extruding the resin composition of any one of claims 1-14 at 120-250 ℃; and in the extrusion molding process, the temperature of the die is the melting point of the polyolefin elastomer to 220 ℃.
20. The article of claim 18, wherein said article is used to prepare a rubber-plastic article selected from the group consisting of: wear-resistant soles, puncture-resistant films, shock absorbers, foaming materials, conveyor belts, toughened and modified polypropylene or nylon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002146112A (en) * | 2000-11-08 | 2002-05-22 | Sumitomo Wiring Syst Ltd | Olefinic thermoplastic elastomer composition |
| CN102030844A (en) * | 2010-09-14 | 2011-04-27 | 中国科学院上海有机化学研究所 | Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight |
| CN113912758A (en) * | 2020-06-23 | 2022-01-11 | 中国科学院上海有机化学研究所 | Ultra-high molecular weight polyethylene and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002146112A (en) * | 2000-11-08 | 2002-05-22 | Sumitomo Wiring Syst Ltd | Olefinic thermoplastic elastomer composition |
| CN102030844A (en) * | 2010-09-14 | 2011-04-27 | 中国科学院上海有机化学研究所 | Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight |
| CN113912758A (en) * | 2020-06-23 | 2022-01-11 | 中国科学院上海有机化学研究所 | Ultra-high molecular weight polyethylene and preparation thereof |
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