CN114907638A - Polyolefin elastomer/low-branched ultrahigh molecular weight polyethylene resin composition and preparation method thereof - Google Patents
Polyolefin elastomer/low-branched ultrahigh molecular weight polyethylene resin composition and preparation method thereof Download PDFInfo
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- CN114907638A CN114907638A CN202110172678.8A CN202110172678A CN114907638A CN 114907638 A CN114907638 A CN 114907638A CN 202110172678 A CN202110172678 A CN 202110172678A CN 114907638 A CN114907638 A CN 114907638A
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- polyolefin elastomer
- weight polyethylene
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- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 72
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 70
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 70
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000001746 injection moulding Methods 0.000 claims abstract description 26
- -1 polypropylene Polymers 0.000 claims abstract description 16
- 239000002121 nanofiber Substances 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000002787 reinforcement Effects 0.000 claims abstract description 6
- 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 41
- 238000000465 moulding Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 229920001971 elastomer Polymers 0.000 claims description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000000520 microinjection Methods 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000006096 absorbing agent Substances 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
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000006261 foam material Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 238000005187 foaming Methods 0.000 abstract description 5
- 238000007723 die pressing method Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 30
- 239000002131 composite material Substances 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 18
- 239000000835 fiber Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
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- 239000000463 material Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 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
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000001276 controlling effect Effects 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
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 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
- 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 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 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
- 238000005481 NMR spectroscopy Methods 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000000805 composite resin Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006073 displacement reaction 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
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 238000001891 gel spinning Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000012943 hotmelt Substances 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
- 238000007689 inspection 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
- 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
- 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
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- 230000035484 reaction time Effects 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
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- 238000003856 thermoforming Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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Classifications
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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
- 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
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- 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
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- 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: 80-99.9 wt% of polyolefin elastomer and 0.1-20 wt% of low-branched ultrahigh molecular weight polyethylene dispersed phase reinforcement (degree of branching is less than 1/100000C). The low-branched ultrahigh molecular weight polyethylene in-situ micro-nano fiber provided by the invention can simultaneously improve the rigidity and strength of the polyolefin elastomer, and injection molding, die pressing and extrusion molding products manufactured by combining with other additives can be applied to the fields of wear resistance, puncture resistance, shock absorption, light foaming, conveyor belts, toughening modification of polypropylene and nylon and the like.
Description
Technical Field
The invention belongs to the technical field of modification and processing forming of high polymer materials, and particularly relates to an in-situ formed low-branched ultra-high-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, molecular weight and long-chain branch content of the 'cutting' comonomer in a molecular chain, the aggregation structure of POE and the corresponding thermal, mechanical and rheological properties of the POE can be regulated and controlled. POE is a copolymer of amorphous soft segments and crystallizable hard segments chemically bonded together. The thermodynamic incompatibility of the different segments leads to the formation of a heterogeneous aggregated structure. At the use temperature, the amorphous soft segment provides elasticity of the rubber, and the crystals with reversible hot melt and cold cure serve as physical crosslinking points to provide mechanical strength. At high temperature, the crystals melt to have thermoplasticity, and thus are processed using processing equipment such as injection molding, extrusion, and foaming 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 little pollution, is nontoxic and can be recycled. Besides automobile tires, POE is widely applied to interior and exterior trims of automobiles, wire and cable sheaths, building waterproof coiled materials, biomedical materials, household appliances, photovoltaic packaging, soles, bicycle tires and the like. However, due to the limitations of high temperature (non) metallocene catalysts and high temperature and pressure solution copolymerization technology, 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.
The molecular weight of the ultra-high molecular weight polyethylene (UHMWPE) is 1-9 × 10 6 g/mol, high chain entanglement content, self-lubrication, abrasion resistance, cutting resistance, low-temperature impact resistance, environmental stress crack resistance, scale deposition resistance, pollution resistance and excellent biocompatibility. Therefore, the high-strength and high-modulus UHMWPE fibers manufactured by solution gel spinning are widely applied to cut-resistant protective gloves, bulletproof vests and boatsThe cable is only used, materials manufactured through compression molding and extrusion are applied to artificial joints and special plates through one-time molding or secondary processing, the pipe manufactured through a single-screw extrusion method is applied to the fields of wear resistance and high temperature resistance, and the UHMWPE microporous membrane manufactured through heat-to-phase separation and unidirectional stretching is applied to a lithium battery diaphragm. UHMWPE is used as high-performance engineering plastic, and is also applied to toughening, reinforcing and modifying polypropylene and wear-resisting and modifying 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 mainly manufactured by two ways, the first is that the friction resistance of the rubber can be obviously improved by adding the chopped UHMWPE fibers in the rubber mixing process (CN 1454928A). However, when the vulcanization or molding temperature is higher than the melting point of the fiber, the fiber melts and the reinforcing effect is reduced. In addition, the chopped fibers have smooth surfaces, are not easy to adhere foreign matters, and have low bonding strength with the 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 interfacial modification method to increase the degree of bonding 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 by interfacial modification technique, although the tear strength of the composite and the peel strength of the fibers are both improved, the tensile modulus of the composite is lower. Aizezi M. et al (ACS appl. Polym. Mater.2019,1,7,1735-1748) melt-blend polyolefin elastomer particles with polypropylene resin to form a bicontinuous phase structure, improve the phase interface between the polyolefin elastomer and the polypropylene by radiation crosslinking, and orient the polypropylene dispersed phase by secondary die pressing, so that the 100% elongation at break and the tensile strength of the prepared film are significantly improved compared with the uncrosslinked blend. The rubber composite material with excellent comprehensive performance is prepared by chemically grafting and modifying the surface of the chopped UHMWPE fiber in Zhanglian group of Beijing chemical university. In conclusion, the above processes all require the conventional processing of rubber, and the cost of continuously mass-producing manufactured articles is high.
In conclusion, the in-situ formed low-branched ultrahigh molecular weight polyethylene micro-nano fiber reinforced polyolefin elastomer resin composition which is low in cost and suitable for continuous batch production is not available in the field.
Disclosure of Invention
The invention provides a melt blending resin composition which is low in cost and suitable for continuous batch production and is used for forming a low-branched ultrahigh molecular weight polyethylene micro-nano fiber reinforced polyolefin elastomer in situ.
In a first aspect of the present invention, there is provided a melt-blended resin composition, characterized in that the composition comprises:
80 to 99.9 wt.% of a polyolefin elastomer, and
0.1-20 wt% of dispersed phase reinforcement of low-branched ultrahigh molecular weight polyethylene, wherein the branching degree of the low-branched ultrahigh molecular weight polyethylene is less than 1/100000 ℃.
In another preferred example, the morphology of the powder of the low-branched ultrahigh molecular weight polyethylene is irregular or spheroidal particles, and the low-branched ultrahigh molecular weight polyethylene is composed of secondary spheroidal particles connected by nanofibers.
In another preferred embodiment, the low-branched ultrahigh molecular weight polyethylene further has one or more characteristics selected from the group consisting of:
viscosity average molecular weight of 1.0-9 × 10 6 g/mol；
The particle size is 40-300 μm;
the melting point of the powder is 140-145 ℃;
the crystallinity is 65-80 wt%.
In another preferred example, the thickness of the in-situ formed low-branched ultrahigh molecular weight polyethylene micro-nano fiber in the composition is 50 nm-1 um.
In another preferred embodiment, the size of the irregular particles of the low-branched ultrahigh molecular weight polyethylene in the composition is 100nm to 50 um.
In another preferred embodiment, the polyolefin elastomer is an ethylene/a-olefin copolymer containing up to 50% by weight of a-olefin.
In another preferred embodiment, the polyolefin elastomer is selected from the group consisting of: engage of Dow company TM Tafmer series brand, Mitsui Chemical Co TM Serial brand, ExxonMobileCompany VistaMaxx TM Lucene of LG company, series brand TM Serial brand and Fortify of SABIC TM A series of branded products, or a combination thereof.
In another preferred embodiment, in the polyolefin elastomer, 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, 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 (2.16kg @190 ℃) and a density of 0.85 to 0.90g/cm 3 The content of the comonomer is less than or equal to 50wt percent.
In another preferred embodiment, the melting point of the polyolefin elastomer is 30-120 ℃, and the glass transition temperature is-60 to-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:
optional (1) premixing: uniformly mixing polyolefin elastomer particles and low-branched ultrahigh molecular weight polyethylene powder;
(2) melt blending: melt blending the polyolefin elastomer particles and the low-branched ultrahigh molecular weight polyethylene powder in a melt blending device, wherein the blending is carried out at a temperature which is higher than the melting point of the polyolefin elastomer and lower than the decomposition temperature of the polyethylene, and the rotating speed of the melt blending device is 50-500 rpm; preferably, after blending is complete, the resin composition is pelletized.
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 equipment is selected from the group consisting of: a reverse twin-screw extruder, an in-phase twin-screw extruder, and a single-screw extruder.
In another preferred embodiment, the blending temperature is 80-250 ℃.
In another preferred embodiment, the rotation speed of the melt blending device is 200-500 rpm.
In a third aspect of the invention, there is provided an article prepared from or containing a resin composition according to the first aspect of the invention.
In a fourth aspect of the invention, there is provided a method of manufacturing an article according to the third aspect of the invention, the article being shaped by a method selected from the group (i), (ii) or (iii) below:
(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: subjecting the resin composition according to the first aspect of the present invention to compression molding at a molding temperature of 190 ℃ or lower and above the melting point of the polyolefin elastomer;
(iii) and (3) extrusion molding: the resin composition according to the first aspect of the present invention is extrusion-molded at 120-250 ℃; and in the extrusion molding process, the temperature of the die is-220 ℃ of the melting point of the polyolefin elastomer.
In another preferred example, the ultrahigh molecular weight polyethylene in the injection molding, die pressing and extrusion molding product is in a micro-nano fibrous shape and a spherical-like micro-nano particle shape.
In another preferred example, when the injection molding process is used, the tensile modulus of the resin composition is improved by 2 to 40 times as compared to a pure polyolefin elastomer.
In another preferred embodiment, when the injection molding process is used, the 100% tensile strength of the resin composition is improved by 1 to 5 times as compared to a pure polyolefin elastomer.
In another preferred example, when the compression molding process is used, the tensile modulus of the resin composition is improved by 2 to 35 times as compared to a pure polyolefin elastomer.
In another preferred example, when the compression molding process is used, the 100% tensile strength of the resin composition is improved by 1 to 4 times as compared with that of a pure polyolefin elastomer.
In another preferred embodiment, the product is used for preparing a rubber plastic product selected from the following group: wear-resistant soles, puncture-resistant films, shock absorbers, foam materials, conveyor belts and toughening modification of polypropylene or nylon.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a diagram of the morphology of a low-branching ultra-high molecular weight polyethylene powder used in the present invention;
FIG. 2 is a tensile stress-strain curve of micro-injection molded and extruded composites of examples 2.1-3 and 3.1-3.4 of the present invention;
fig. 3 is a morphology diagram of the low-branched ultrahigh molecular weight polyethylene micro-nano fibers in the injection-molded and die-molded sheets of examples 2.1, 3.2 and 3.4 of the present invention.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time to develop a resin composition comprising a polyolefin elastomer and a dispersed phase reinforcement of a low-branched ultrahigh molecular weight polyethylene. By adjusting the content of the dispersed phase reinforcement of the low-branched ultrahigh molecular weight polyethylene, 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 ultrahigh molecular weight polyethylene chopped fiber reinforced rubber composite material and the processing method thereof, the invention provides an in-situ formed low-branched ultrahigh molecular weight polyethylene micro-nano fiber reinforced polyolefin elastomer composition and a preparation method thereof, wherein the method comprises the following steps:
(1) pre-mixing: the polyolefin elastomer particles and the ultra-high molecular weight polyethylene powder weighed in proportion are mixed uniformly using a high-speed mixer or other mixing equipment. The premixing process section can also be omitted by feeding in batches through a twin-screw extruder.
(2) Melt blending: melt blending is carried out by a double-screw extruder, the blending temperature is 100-250 ℃, the rotating speed is 100-500rpm, and granulation is carried out.
(3) Molding: the molding is carried out by adopting any one of the following methods:
injection molding: the injection temperature is 100-250 ℃, the mold temperature is 0-80 ℃, and the tensile modulus and 100% definite elongation strength of the composition are respectively improved by 40 times and 5 times compared with those of the pure polyolefin elastomer.
Compression molding: the composite is molded by compression at the molding temperature above the melting point of the polyolefin elastomer and below 190 ℃, and the tensile modulus and the 100 percent definite elongation strength of the composite are respectively improved by 35 times and 4 times compared with the pure polyolefin elastomer.
The ultrahigh molecular weight polyethylene powder in the step 1 is irregular or sphere-like loose porous powder, contains sphere-like secondary particles (figure 1) connected by nano fibers, has a branching degree of less than 1/100000C, and has a viscosity-average molecular weight of 1.5-9 × 10 6 g/mol, particle size of 40-300 um, powder melting point of 140-145 ℃, and crystallinity of 65-80 wt%.
The polyolefin elastomer particles described in step 1 are an ethylene/a-olefin copolymer containing up to 50% by weight of an a-olefin, the a-olefin being propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., preferably an ethylene/1-butene copolymer and an ethylene/1-octene copolymer, having a melt flow index of 0.2 to 30g/10min (2.16kg @190 ℃), a weight average molecular weight of 50 to 300kg/mol, a molecular weight distribution of 1.5 to 3, and a density of 0.85 to 0.92g/cm 3 The melting point is 30-120 deg.C, and the glass transition temperature is-60 deg.C to-30 deg.C. The polyolefin elastomer product may be selected from Engage of Dow corporation TM Tafmer series brand, Mitsui Chemical Co TM VistaMaxx series brand, VistaMaxx by ExxonMobile TM Lucene of series brand and LG company TM Serial brand and Fortify of SABIC TM Series brands of products and compositions thereof.
The process described in steps 2 and 3 may be carried out in a twin-screw extruder, which may preferably be a counter-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 is molded to prepare related products, such as wear-resistant soles, puncture-resistant films, shock absorbers, foaming materials, conveyor belts and other fields, and can also be applied to toughening modification of polypropylene and nylon.
Low-branching ultra-high molecular weight polyethylene as reinforcement
The low-branched ultra-high molecular weight polyethylene used in the present invention may be prepared by methods known in the art, and in a preferred embodiment, by the following method:
the heterogeneous catalyst system comprising catalyst and alkyl aluminum compound as cocatalyst is contacted with ethylene and reacted at ethylene partial pressure of 0.2-10 MPa and 0-100 deg.c for 1-18 hr to obtain the catalyst. The molar ratio of the catalyst to the cocatalyst is 1:1-5000, and the polymerization can be carried out for 2-6 hours at 1:10-2000 so as to maintain the catalytic activity, the polymer property and the production cost in a better range, preferably 1: 20-500.
Wherein said catalyst may be prepared by using corresponding catalysts known in the art, but in a preferred embodiment the catalyst is prepared by steps (a) to (d), and optionally step (e):
(a) adding anhydrous magnesium chloride into an inert hydrocarbon solvent under the protection of inert gas, adding C1-C10 alcohol with the weight of magnesium chloride being more than or equal to 2 equivalents under the stirring condition for contact, keeping the system at 60-120 ℃ to form a uniform solution, then cooling to below-30 ℃, and controlling the stirring speed and the rotating speed of a supergravity reactor 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 a C1 to C10 alcohol; more preferably 2 to 4 equivalents;
(b) contacting the precursor slurry I obtained in the step (a) with alkyl aluminum for 1-2h at the temperature of below-30 ℃, and then keeping the temperature at 60-120 ℃ for 2-6h to obtain precursor slurry P-II;
(c) contacting the precursor slurry II obtained in the step (b) with a hydrocarbon solution of a titanium compound at the temperature of below-30 ℃ for 0.5-1h, heating and keeping at the temperature of 60-120 ℃ for 2-6h to obtain catalyst slurry C-III; the temperature rising speed 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 a hydrocarbon solvent, e.g. TiCl 4 Or Ti (R) 4 Wherein R is C1-C6 alkyl, allyl, benzyl or NMe 2 Or other titanium compounds capable of being dissolved 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 complex titanium-carrying reaction of the alkyl complex of the fourth subgroup metal titanium, the reaction temperature rise speed needs to be controlled, wherein the temperature rise speed is 1-10 ℃/min, preferably 1-5 ℃/min, and most preferably 1 ℃/min; the temperature of the final titanium-loaded contact reaction is controlled to be 60-120 ℃, preferably 80-100 ℃, and the reaction time is controlled to be 2-6h, preferably 4-5h at the preferred temperature.
The polymerization is generally carried out in an inert organic solvent, such as hydrocarbons, cyclic hydrocarbons or aromatic hydrocarbons, but also in halogenated solvents, such as dichloroethane, chlorobenzene, in order to facilitate the operation of the reactor, hydrocarbons with less than 12 carbons can be used as inert organic solvent. Examples include, 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 from 0 to 100 ℃ and, for good catalytic activity and productivity, from 40 to 80 ℃.
Better reactor operating parameters and polymers can be obtained by operating at a polymerization ethylene partial pressure of 0.2 to 1.5MPa or a polymerization ethylene partial pressure of 0.2 to 1.5 MPa/hydrogen partial pressure of 0.01 to 0.1 MPa.
The cocatalyst is an alkylaluminum compound, alkylaluminoxane or a weakly coordinating anion; the alkylaluminum compound is preferably AlEt 3 ，AlMe 3 Or Al (i-Bu) 3 ，AlEt 2 Cl, alkylaluminoxane preferably methylaluminoxane, MMAO (modified methylaluminoxane), etc.; weakly coordinating anions are preferably [ B (3,5- (CF) 3 ) 2 C 6 H 3 ) 4 ] - 、 - OSO 2 CF 3 Or ((3,5- (CF) 3 ) 2 )C 6 H 3 ) 4 B - . The catalyst and cocatalyst can be added to the system in any order to allow the polymerization to proceed, preferably AlEt 3 . The ratio of catalyst to cocatalyst used in the polymerization can vary, generally said polymerization time ranges from 1 to 18 hours, the molar ratio of catalyst to cocatalyst is from 1:1 to 5000, and polymerization can generally be carried out at a time of from 1:10 to 2000 for from 2 to 6 hours in order to maintain the catalytic activity, the polymer properties and the production costs in a good range, preferably from 1:20 to 500.
In a preferred embodiment of the invention, the catalyst catalyzes ethylene to polymerize at 40-80 ℃ and under the ethylene pressure of 0.2-0.8MPa to obtain ultra-high molecular weight polyethylene particles, the polymerization activity is higher than 100Kg PE/g Cat, and the weight ratio of powder obtained by polymerization is at least 95 percent and passes through a 150 micron mesh sieve, and the medium diameter (d) is measured by a laser diffraction scattering method 50 ) D is not less than 50 mu m 50 D is less than or equal to 80 mu m, preferably less than or equal to 50 mu m 50 Less than or equal to 70 mu m, and the viscosity-average molecular weight of the polyethylene is 150-; more preferably, the polyethylene viscosity average molecular weight is 150-800 ten thousand. By melting 13 C NMR analysis of the branched structure 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. according to the invention, a common double-screw extruder is used for directly melt blending the polyolefin elastomer and the low-branched ultrahigh molecular weight polyethylene powder to form an ultrahigh molecular weight polyethylene micro-nano fibrous structure in situ, the micro-nano fibrous structure is retained and oriented by adjusting injection molding and mould pressing processes, and the tensile modulus and the stretching strength of the polyolefin elastomer are greatly improved, so that the rigidity and the strength of the rubber are simultaneously increased.
2. The low-branching ultrahigh 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 ultrahigh molecular weight polyethylene micro-nano fibers.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by weight.
Detailed Description
The specific examples are used for illustrating the superiority of the novel low-branched ultrahigh molecular weight polyethylene in-situ micro-nano fiber reinforced polyolefin elastomer composition and the preparation method thereof and the controllability of the product performance. 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 its morphology in the composition: after vacuum platinization at HITACHI MCI000, the powder morphology and the low temperature brittle fracture profile of the composition were characterized using a HITACHI Regulus 8100 scanning electron microscope at 10KV and 10uA conditions;
melting point and crystallinity testing of the powders: and DSC2000 test is carried out, wherein 3-8mg of powder slices are placed into an aluminum dry pot, the temperature is increased to 160 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, the temperature is kept for 3min, and then the temperature is reduced to 40 ℃ at the cooling rate of 10 ℃/min, and the temperature is kept for 3 min. The temperature is raised to 160 ℃ at a heating rate of 10 ℃/min. The crystallinity is the melting enthalpy 100%/290 (KJ/mol).
And (3) testing mechanical properties: injection molded samples were prepared according to the examples and injection molded into ISO20573-TypeCP multipurpose bars. The molded sheets were cut using a punch and cutter to ISO20573-TypeCP multipurpose bars. The test is carried out in a WDW-20 electronic universal tester, the stretching speed is 50mm/min, the environmental temperature is 23 ℃, and the mechanical property data is the average value of 5-6 samples.
And (3) testing composite viscosity: low temperature molded samples were cut into 25mm diameter disks and the complex viscosity was measured in a TA Instrument ARES-G2 rotational rheometer at 160 ℃ in the range of 0.01 to 100 rad/s.
The twin-screw extruder and the microinjection molding used in the present invention were a HAAKE PolyLab OS RheoDrive 4 twin-screw extruder (L/D40) and a HAAKE MiniJet II injection molding machine from Thermo Scientific. The molding press is an XH-406 type universal tablet press manufactured by Xihua precision inspection Instrument Co., Ltd, and has two independent heating and pressurizing units, the molding is performed in the lower unit, and the cooling crystallization is performed in the upper unit. The mechanical property test uses ISO20573-TypeCP multipurpose spline.
The raw material used in the invention is low-branched ultra-high molecular weight polyethylene, a pilot product with the number of UH and the viscosity-average molecular weight of 3.89 multiplied by 10 6 g/mol, melting point 142.5 ℃, crystallinity 81.7%, degree of branching < 1/100000, and powder form as shown in FIG. 1. The low-branched ultrahigh molecular weight polyethylene can be prepared by any suitable method known in the art, such as the low-branched ultrahigh molecular weight polyethylene described in chinese patent 201010554473.8.
In a preferred embodiment, the low-branched ultra-high molecular weight polyethylene is prepared by the following method:
sequentially using N in a 30L stainless steel stirring polymerization kettle 2 Displacement, AlEt with 8kg of hexane under 0.4MPa of nitrogen 3 (10mL) is added into a kettle, the stirring speed is controlled to be 250rpm, the temperature in the kettle is preheated to about 60 ℃, then 30mg of Cat is flushed into a polymerization kettle by using 2kg of hexane under the condition of 0.4MPa of nitrogen pressure, the activation is carried out for 10min, then the nitrogen pressure in the kettle is removed, ethylene gas is introduced to ensure that the pressure in the kettle reaches 0.4MPa, the temperature in the kettle is controlled to be 70 ℃, the ethylene introduction is stopped after the polymerization is carried out for 2h, the temperature in the kettle is reduced to below 50 ℃ by using a circulating constant-temperature oil bath, the gas in a system is discharged, and the granular polymer is obtained after drying. Wherein, the catalyst is prepared by the following method:
(a) adding anhydrous magnesium chloride into an inert hydrocarbon solvent under the protection of inert gas, adding C1-C10 alcohol with the weight of magnesium chloride being more than or equal to 2 equivalents under the stirring condition for contact, keeping the system at 60-120 ℃ to form a uniform solution, then cooling to below-30 ℃, and controlling the stirring speed and the rotating speed of a supergravity reactor 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 alkyl aluminum for 1-2h at the temperature of below-30 ℃, and then keeping the temperature at 60-120 ℃ for 2-6h to obtain precursor slurry P-II;
(c) contacting the precursor slurry II obtained in the step (b) with a hydrocarbon solution of a titanium compound at the temperature of below-30 ℃ for 0.5 to 1 hour, heating and keeping the temperature at 60 to 120 ℃ for 2 to 6 hours to obtain catalyst slurry C-III; the temperature rising speed 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 present invention are Engage of the Dow chemical company TM The product has a molecular weight of 71.7kg/mol, a molecular weight distribution of 2.27 and a branching degree of 35.1CH 3 The 1-octene content was 8.7 mol%, melting point 78 ℃ for 1000C.
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 feed inlet of a double-screw extruder, blending at the temperature of 190-. And under the same conditions, blending, granulating and drying.
Example 1.2 blend example E2
Weighing 800g of polyolefin elastomer, 200g of ultrahigh molecular weight polyethylene powder and 5g of antioxidant (1010), uniformly premixing, pouring into a feed inlet of a double-screw extruder, blending at the temperature of 110-120-. And under the same conditions, blending, granulating and drying.
Example 1.3 blending example E3
Weighing 800g of polyolefin elastomer, 200g of ultrahigh molecular weight polyethylene powder and 5g of antioxidant (1010), uniformly premixing, pouring into a feed inlet of a double-screw extruder, blending at the temperature of 140-. And under the same conditions, blending, granulating and drying.
Example 1.4 blend example E4
Weighing 900g of polyolefin elastomer, 100g of ultra-high molecular weight polyethylene powder and 5g of antioxidant (1010), uniformly premixing, pouring into a feed inlet of a double-screw extruder, blending at the temperature of 110-. And under the same conditions, blending, granulating and drying.
Example 1.5 blend example E5
900g of polyolefin elastomer, 100g of ultrahigh molecular weight polyethylene powder and 5g of antioxidant (1010) are weighed, uniformly premixed and poured into a feeding port of a double-screw extruder. The temperature from the feeding section of the extruder to the die orifice is 110-130-125 ℃, the rotation speed is 100rpm, the torque is 80-100Nm, the feeding rate is 6-8%, the extruder is cooled in a water bath after extrusion, granulated and dried in vacuum at 60 ℃ for 24 h.
COMPARATIVE EXAMPLE 1.1 blending COMPARATIVE EXAMPLE E6
Weighing 1000g of polyolefin elastomer and 5g of antioxidant (1010), uniformly premixing, pouring into a feeding port of a double-screw extruder, extruding at the temperature of 140-160-170-190-180-170 ℃, at the rotation speed of 150rpm, at the torque of 75Nm and at the feeding rate of 15%, cooling in a water bath after extrusion, granulating, and vacuum drying at the temperature of 60 ℃ for 24 h. And under the same conditions, blending, granulating and drying.
Example 2.1 injection Molding example IM1
Using the granulated composition of E1, ISO20573-TypeCP multipurpose sample bars were prepared by injection molding in Thermo Scientific HAAKE MiniJet II at 220 ℃ under 90MPa for 30s, 60MPa for 1min for 40 ℃ for crystallization time 5 min.
Example 2.2 injection moulding example IM2
Using the granulated composition of E4, ISO20573-TypeCP multipurpose sample bars were prepared by injection molding in Thermo Scientific HAAKE MiniJet II at 125 ℃ under 90MPa for 30s, 60MPa for 1min for 40 ℃ for crystallization time 5 min.
Example 2.3 injection Molding example IM3
Using the granulated composition of E2, ISO20573-TypeCP multipurpose sample bars were prepared by injection molding in Thermo Scientific HAAKE MiniJet II at 135 ℃ under 90MPa for 30s, 60MPa for 1min for 40 ℃ for crystallization time 5 min.
Comparative example 2.1 injection moulding comparative example IM4
Using the E6 pelletized polyolefin elastomer, ISO20573-TypeCP multipurpose specimens were prepared by injection molding in Thermo Scientific HAAKE MiniJet II at 160 ℃ under 90MPa for 30s, 60MPa for 1min, 40 ℃ for the mold and 5min for the crystallization time.
EXAMPLE 3.1 moulding example CM1-3
The composition granulated by E2 was pre-pressed at 125, 135, 142 deg.C and the same 2.5MPa for 10min, then pressed at 10MPa for 5min, cooled and crystallized at 40-60 deg.C for 5-10min, and a sheet having a thickness of 2mm was prepared. Standard bars were prepared 5-6 using a die cutter and an ISO20573-TypeCP cutter.
EXAMPLE 3.2 moulding example CM4-6
The composition granulated using E3 was precompacted in a moulding press at 120, 125, 135 ℃ and the same 2.5MPa for 10min, pressed again at 10MPa for 5min, cooled to 40-60 ℃ for 5-10min to prepare a sheet having a thickness of 2mm, a composite viscosity at 10rad/s and 120 ℃ of 13.5 kPa.s. Standard bars were prepared 5-6 using a die cutter and an ISO20573-TypeCP cutter.
EXAMPLE 3.3 moulding example CM7
The composition granulated with E1 was pre-pressed in a molding press at 120 ℃ and 2.5MPa for 10min, then pressed at 10MPa for 5min, cooled and crystallized at 60 ℃ for 5-10min to prepare a sheet having a thickness of 2 mm. Standard bars were prepared 5-6 using a die cutter and an ISO20573-TypeCP cutter.
EXAMPLE 3.4 moulding example CM8-9
The composition granulated with E4 and E5 was precompressed in a molding press at 123 ℃ and 2.5MPa for 10min, and then pressed at 10MPa for 5min, and cooled to 40-60 ℃ for crystallization for 5-10min to prepare a sheet having a thickness of 2 mm. The composite viscosity at 10rad/s and 120 ℃ is 7.42 kPa.s. Standard bars were prepared 5-6 using a die cutter and an ISO20573-TypeCP cutter.
COMPARATIVE EXAMPLE 3.1 compression-molded COMPARATIVE EXAMPLE CM10
The polyolefin elastomer pelletized using E6 was preliminarily pressed at 125 ℃ and 2.5MPa in a molding press for 10min, and further pressed at 10MPa for 5min, cooled and crystallized at 40 ℃ for 10min to prepare a sheet having a thickness of 2mm and a complex viscosity at 10rad/s and 120 ℃ of 4.54 kPa.s. Standard bars were prepared 5-6 using a die cutter and an ISO20573-TypeCP cutter.
The test results of the samples prepared in the above respective examples are shown in the following table 1:
TABLE 1
The results of the blending examples 1.1 to 6 and the micro injection molding examples 2.1 to 3 show that when the polyolefin elastomer is blended with the low-branched high molecular weight polyethylene at a high temperature, the twin-screw torque is not large (example 1.1), and when the polyolefin elastomer is blended at a low temperature according to the in-situ micro-nano fiber technology, the torque is large (examples 1.2 and 1.5), the rotating speed of the extruder needs to be reduced so as to reduce the melt viscosity of the composition and the extrusion friction heat, which results in reduction of the production efficiency and unsuitability for mass production, and more importantly, the reduction of the rotating speed of the extruder reduces the shear rate, so that the dispersibility of the ultra-high molecular weight polyethylene powder is poor. Significantly, however, such low temperature blended pellets, when low temperature injection molded, the composite retained a stiff elastic behavior without exhibiting significant yield behavior (example 2.3-IM3 and FIG. 2-IM3 curves). When the ultrahigh molecular weight polyethylene is blended above the melting point and injected at low temperature, only 10 wt% of the ultrahigh molecular weight polyethylene needs to be added, so that the performance of the composite material can be greatly improved (example 2.2 and attached figure 2-IM 2). Therefore, when polyolefin elastomers are blended with low-branched ultrahigh molecular weight polyethylene and processed, it is necessary to balance the processability and the properties of the article.
As shown in table 1, when the molding temperature (mold temperature) is reduced to a temperature (125-:
(1) results of micro-injection molding 2.1-2.3 (Table 1) show that when the content of the low-branched ultra-high molecular weight polyethylene in the polyolefin elastomer matrix exceeds 10 wt%, the skin of the injection molded composite material is easy to form a physical network of three-dimensional chain entanglement, micro-nano fibers are oriented (figure 3, POE20UH-IM), and the composite material still shows yield behavior even when injection molded at high temperature (examples 2.1-3 and figure 2-IM). Thus, the content of the low-branched ultra-high molecular weight polyethylene should be less than 20 wt%, more preferably less than 10 wt%, taking into account the processability and the elastic properties as well as the abrasion resistance of the composite.
(2) The results of molding examples 3.1 to 3.4 (Table 1) show that when the molding temperature is higher than the melting point of the polyolefin elastomer and close to the melting point of the low-branched ultrahigh-molecular-weight polyethylene powder, the low-branched ultrahigh-molecular-weight polyethylene retains the nanofiber structure (FIG. 3, POE10UH-CM and POEUH-CM), the mechanical properties in the composite material are remarkably enhanced, and the composite material retains the properties of a hard elastomer; with the increase of the content of the ultra-high molecular weight polyethylene and the increase of the molding temperature, the tensile modulus and the elongation at break of the composite material are improved, but the increase of the molding temperature is favorable for the bonding between particles. When the content of the low-branched ultrahigh molecular weight polyethylene in the polyolefin elastomer matrix exceeds 20 wt%, the mechanical property of the molded composite material is greatly increased, but the three-dimensional chain entanglement network greatly increases the composite viscosity of the composition, and the melt flow property of the composition is influenced. Therefore, the processability, the elastic property, the abrasion resistance and the like of the composite material are considered, and the content of the low-branched ultrahigh molecular weight polyethylene is less than 20 wt%. The rheological property of the molding material is tested by using an ARES-G2 rheometer, and the composite viscosities of POE20UH, POE10UH and POE at 0.1rad/s are respectively 49, 9.3 and 4.8kP.s, which shows that the addition of the 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 elastomers and foaming materials thereof.
By combining the above, when the composition is applied to industrial production, the blending and processing forming processes are optimized, so that the dosage of the low-branched ultrahigh molecular weight polyethylene can be obviously reduced, and the production cost is reduced. According to the performance requirements (elasticity, rigidity and abrasion resistance special performance) of the composite material, the composite resin containing different components of ultra-high molecular weight polyethylene can be selected to meet the requirements of production and products.
All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A melt-blended resin composition, comprising:
80 to 99.9 wt.% of a polyolefin elastomer, and
0.1-20 wt% of dispersed phase reinforcement of low-branched ultrahigh molecular weight polyethylene, wherein the branching degree of the low-branched ultrahigh molecular weight polyethylene is less than 1/100000 ℃.
2. The resin composition of claim 1, wherein the powder morphology of the low-branched ultrahigh molecular weight polyethylene is irregular or spheroidal particles, and the low-branched ultrahigh molecular weight polyethylene consists of secondary spheroidal particles connected by nanofibers.
3. The melt blended resin composition of claim 1 or 2, wherein said low-branched, ultra-high molecular weight polyethylene further has one or more characteristics selected from the group consisting of:
viscosity average molecular weight of 1.0-9 × 10 6 g/mol；
The particle size is 40-300 μm;
the melting point of the powder is 140-145 ℃;
the crystallinity is 65-80 wt%.
4. The melt blended resin composition of claim 1, wherein said polyolefin elastomer is an ethylene/a-olefin copolymer containing up to 50 weight percent of an a-olefin.
5. The resin composition according to claim 1 or 4, wherein the a-olefin in the polyolefin elastomer 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.
6. The method for preparing a resin composition according to claim 1, comprising the steps of:
optionally (1) premixing: uniformly mixing polyolefin elastomer particles and low-branched ultrahigh molecular weight polyethylene powder;
(2) melt blending: melt blending the polyolefin elastomer particles and the low-branched ultrahigh molecular weight polyethylene powder in a melt blending device, wherein the blending is carried out at a temperature which is higher than the melting point of the polyolefin elastomer and lower than the decomposition temperature of the polyethylene, and the rotating speed of the melt blending device is 50-500 rpm; preferably, after blending is complete, the resin composition is pelletized.
7. The method of claim 6, wherein the temperature of the blending is from 80 ℃ to 250 ℃.
8. An article prepared from the resin composition of claim 1 or comprising the resin composition of claim 1.
9. The method of claim 8, wherein the article is formed 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 6 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 by press the resin composition according to any one of claims 1 to 6 at a molding temperature of 190 ℃ or higher and above the melting point of the polyolefin elastomer;
(iii) and (3) extrusion molding: extrusion molding the resin composition as claimed in any one of claims 1 to 5 at 120-250 ℃; and in the extrusion molding process, the temperature of the die is-220 ℃ of the melting point of the polyolefin elastomer.
10. The article of claim 8, wherein the article is used to make a rubber plastic article selected from the group consisting of: wear-resistant soles, puncture-resistant films, shock absorbers, foam materials, conveyor belts and toughening modification of polypropylene or nylon.
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Citations (4)
| 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 |
| CN111393755A (en) * | 2019-01-03 | 2020-07-10 | 中国石油天然气股份有限公司 | Polyolefin thermoplastic elastomer and preparation method thereof |
| 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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Patent Citations (4)
| 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 |
| CN111393755A (en) * | 2019-01-03 | 2020-07-10 | 中国石油天然气股份有限公司 | Polyolefin thermoplastic elastomer and preparation method thereof |
| 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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