CN117624434A - Ternary polymerization EVA elastomer and preparation method thereof - Google Patents
Ternary polymerization EVA elastomer and preparation method thereof Download PDFInfo
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- CN117624434A CN117624434A CN202311706728.1A CN202311706728A CN117624434A CN 117624434 A CN117624434 A CN 117624434A CN 202311706728 A CN202311706728 A CN 202311706728A CN 117624434 A CN117624434 A CN 117624434A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000000806 elastomer Substances 0.000 title claims abstract description 64
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 5
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 229920006027 ternary co-polymer Polymers 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims 1
- 238000005502 peroxidation Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000005191 phase separation Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 238000002464 physical blending Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 55
- 239000005038 ethylene vinyl acetate Substances 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005187 foaming Methods 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000010985 leather Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 azodiisoheptonitrile Chemical compound 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 101000969770 Homo sapiens Myelin protein zero-like protein 2 Proteins 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- 102100021272 Myelin protein zero-like protein 2 Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of high polymer elastomer materials, in particular to a ternary polymerization EVA elastomer, a preparation method and application thereof. The ternary polymerization EVA elastomer is formed by copolymerizing vinyl acetate, ethylene and a third monomer, wherein the molar ratio of the vinyl acetate to the ethylene is 0.1-500: 0.1 to 1:0.1 to 100. According to the EVA elastomer, units such as hexene are introduced into the EVA elastomer by a ternary polymerization method, so that various performances of the EVA elastomer are enhanced, the phenomena that the EVA elastomer subjected to physical blending modification in the prior art is low in stability, easy to phase separation, and capable of affecting the overall material performance and limiting the application field are avoided, and a polymer elastomer product with excellent mechanical properties and stability, which can be used in the fields of shoe wear, plastic toughening modification, cosmetic packaging and the like, is prepared.
Description
Technical Field
The invention relates to the field of high polymer elastomer materials, in particular to a ternary polymerization EVA elastomer, a preparation method and application thereof.
Background
In recent years, ethylene-vinyl acetate copolymers (EVA) have been widely used in the fields of footwear, packaging, agricultural films, cables, aerospace, solar energy, etc., because of their excellent properties of elasticity, flexibility, adhesion, weather resistance, corrosion resistance, etc. On the other hand, the EVA material can be used for the modification of common plastics such as PE, PVC and the like because of secondary processing such as blow molding, foaming and the like, so that the application frequency of the EVA material is further enhanced, and the performance requirements on the EVA elastomer material are gradually improved by the application.
Because of the higher Vac content, the EVA elastomer has lower crystallinity and linearity, has more advantages in the aspects of tensile strength, low temperature resistance, stress cracking resistance, oil stain resistance and the like compared with the traditional EVA resin, and has good transparency and good elasticity, and the EVA elastomer has more applications in the aspects of rubber elastomer, PVC modification, adhesive and the like compared with the EVA resin. Prior art, chinese paper: physical and mechanical properties research [ J ] of elastomer for leather powder composite EVA shoes, leather and chemical engineering, 2023,40 (01), zhang Wentao and the like research the feasibility of preparing foaming materials from composite materials of leather powder and EVA, and the foaming materials have optimal mechanical properties when the addition amount of the leather powder is 15 percent. Chinese patent: CN116284948A provides a method for preparing a modified EVA elastomer, which enhances the mechanical properties of the EVA elastomer by blending polyborosiloxane with EVA. It can be seen that in the prior art, a blending modification method is mostly adopted for modifying the EVA elastomer, and the method can partially improve the mechanical property of EVA, but also has the defects of low stability, easy phase separation, influence on the overall material property and limitation of the application field. And the demand of the EVA on the market is basically concentrated on EVA with VA content of 20-50%, and the EVA elastomer product with VA content in the range of 50-80% is lacked.
Therefore, in order to thoroughly solve the problems, the invention provides the ternary polymerization EVA elastomer and the preparation method thereof, which can ensure that the VA content of the EVA elastomer is in the range of 60-80%, and fill the market gap.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a ternary polymerization EVA elastomer, which at least includes the following 2 structural units:
the ternary polymerization EVA elastomer also comprises any one of the following 2 structural formula units:
wherein m, n and o are respectively the mole numbers of the ternary polymerization EVA elastomer in the formula 1,2,3 or the formula 1,2, 4.
As a preferable scheme, the molar ratio of m, n and o is 0.1-500: 0.1 to 100:0.1 to 100.
As a preferable scheme, the molar ratio of m, n and o is 1-10: 1 to 10:0.1 to 1.
As a preferred scheme, the molar ratio of m, n and o is 10:3:1.
the second aspect of the invention provides a preparation method of the ternary polymerization EVA elastomer, which comprises the following steps: s1: dissolving an initiator in the vinyl acetate subjected to the water removal treatment for later use; s2: sealing and heating the reaction vessel to 90-110 ℃, pumping and replacing nitrogen atmosphere for three times, vacuumizing and maintaining pressure for 10-12 hours, then heating to 90-110 ℃ in vacuum, filling nitrogen atmosphere, vacuumizing again, repeating for 2-4 times, finally filling ethylene to completely replace nitrogen, and cooling to the reaction temperature; s3: adding solvent, vinyl acetate containing initiator and hexene into a reaction container under stirring, pressurizing nitrogen to reaction pressure, closing ethylene gas inlet after reacting for a period of time, closing a valve to remove ethylene pressure after stopping reacting, reducing rotating speed, injecting a quenching agent, and cooling to below 10 ℃; s4: taking out the obtained reaction product, stirring at normal temperature, and then carrying out the steps of precipitation washing, press drying and vacuum drying.
As a preferable scheme, the reaction temperature in the step S3 is 60-80 ℃; the reaction pressure is 0.1-10 MPa; the reaction time is 4-6 h.
As a preferable scheme, the reaction temperature in the step S3 is 62-70 ℃; the reaction pressure is 3-4.5 MPa; the reaction time is 5-6 h.
As a preferred embodiment, the reaction temperature in the step S3 is 62 ℃; the reaction pressure is 3MPa; the reaction time was 6h.
As a preferable scheme, the quenching agent is ethanol solution of hydroquinone, and the volume ratio of the addition amount to the solvent is 1-1.5: 40-80.
As a preferable scheme, the quenching agent is ethanol solution of hydroquinone, and the volume ratio of the adding amount to the solvent is 1:60.
as a preferable mode, the solvent is any one of a C1-C6 alcohol solvent, a saturated aliphatic solvent, a halogenated hydrocarbon solvent, a cycloalkane solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, an aldehyde solvent, and a furan solvent.
As a preferable scheme, the C1-C6 alcohol solvent is any one of methanol, ethanol, propanol, isopropanol, n-butanol, tertiary butanol, isobutanol, n-pentanol and n-hexanol.
As a preferable embodiment, the saturated aliphatic solvent is any one of hexane, n-heptane, n-octane, n-decane, n-dodecane, and isododecane.
As a preferable scheme, the halogenated hydrocarbon solvent is any one of chloromethane, dichloromethane, trichloromethane, carbon tetrachloride, bromoethane, chloro-n-butane, bromo-n-butane and iodo-n-butane.
As a preferred embodiment, the cycloalkane solvent is cyclohexane or methylcyclohexane.
As a preferable embodiment, the aromatic hydrocarbon solvent is any one of benzene, toluene, ethylbenzene, xylene, and cumene.
As a preferable embodiment, the ester solvent is any one of methyl acetate, ethyl acetate, dimethyl carbonate, and diethyl carbonate.
As a preferred embodiment, the ketone solvent is acetone or butanone.
As a preferred embodiment, the aldehyde solvent is acetaldehyde or crotonaldehyde.
As a preferred embodiment, the furan-based solvent is tetrahydrofuran.
As a more preferred embodiment, the solvent is methanol.
As a preferable embodiment, the initiator is at least one of azo-type initiator and peroxide-type initiator.
As a preferable scheme, the azo initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate and azobis (2-methylbutyronitrile).
As a preferable scheme, the peroxide initiator is at least one of hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, diisobutyryl peroxide, neodecanoate amyl peroxide, amyl valerate peroxide, butyl acetate peroxide and dibutyl peroxydicarbonate.
As a more preferred embodiment, the initiator is azobisisobutyronitrile.
As a preferable scheme, the initiator is added in an amount of 0.1-10% by mass.
In the application, the ternary copolymer EVA elastomer is prepared by adopting a vinyl acetate, ethylene and hexene copolymerization method, and the ternary molar ratio is limited, so that the mechanical property of the EVA elastomer is effectively improved, and the phase separation phenomenon in the prior art is avoided. In particular when the molar ratio of vinyl acetate, ethylene and hexene is 0.1:1:1, the combined action of the three not only effectively improves the overall synthesis efficiency and yield of EVA, but also ensures the ordered arrangement of corresponding units in molecular chains by matching with the preparation method in the application, thereby forming an elastomer molecular chain with good mechanical properties, having proper molecular chain length and increasing the entanglement degree of the molecular chains. In addition, hexene components are introduced into EVA, so that the VA content is ensured, and the defects of low stability, easiness in phase separation, influence on the performance of the whole material and limitation of the application field caused by physical blending modification are avoided.
The third aspect of the invention provides application of the ternary polymerization EVA elastomer, which comprises application of the ternary polymerization EVA elastomer in the fields of shoe wear, plastic toughening and packaging.
The beneficial effects are that:
1. the invention provides an EVA elastomer, which is prepared by introducing hexene units into the EVA elastomer by a ternary polymerization method, and can be used in the fields of shoe wear, plastic toughening modification, cosmetic packaging and the like and has excellent mechanical properties and stability.
2. The invention provides an EVA elastomer, which is also characterized in that hexene units are introduced into the EVA elastomer by a ternary polymerization method to strengthen various performances of the EVA elastomer, so that the phenomena of low stability, easy phase separation, influence on the overall material performance and limitation of application fields, which occur in the prior art of physically blending modified EVA elastomer, are avoided.
3. The EVA elastomer provided by the invention effectively improves the content of VA in the EVA elastomer, and the content can reach 60-80%, fills the gap of EVA elastomer products in the existing market, and has good market prospect.
4. The EVA elastomer provided by the invention has the advantages of simple polymerization reaction conditions, simplicity and convenience in operation and easiness in obtaining raw material cost, greatly reduces labor and raw material cost of enterprise production, and can realize large-scale industrial production and application.
5. The invention provides an EVA elastomer, which effectively improves the mechanical property of the EVA elastomer and avoids the phase separation phenomenon in the prior art by limiting the mole ratio of vinyl acetate, ethylene and hexene; in particular when the molar ratio of vinyl acetate, ethylene and hexene is 0.1:1:1, the combined action of the three not only effectively improves the overall synthesis efficiency and yield of EVA, but also ensures the ordered arrangement of corresponding units in molecular chains by matching with the preparation method in the application, thereby forming an elastomer molecular chain with good mechanical properties, having proper molecular chain length and increasing the entanglement degree of the molecular chains.
Detailed Description
Example 1
Example 1 a first aspect provides a ternary copolymer EVA elastomer comprising 3 structural units:
wherein m, n and o are respectively the mole numbers of the ternary polymerization EVA elastomer in the formulas 1-3, and the mole ratio of m, n and o is 10:3:1.
the preparation method of the ternary polymerization EVA elastomer comprises the following steps: s1: 1.4875g of azodiisobutyronitrile is dissolved in 120mL of vinyl acetate after the dehydration treatment for standby; s2: sealing and heating the reaction vessel to 100 ℃, pumping and replacing nitrogen atmosphere for three times, vacuumizing and maintaining pressure for 10 hours, then heating to 100 ℃ in vacuum, filling nitrogen atmosphere, vacuumizing again, repeating for 3 times, finally filling ethylene to completely replace nitrogen, and cooling to the reaction temperature of 62 ℃; s3: adding 300mL of methanol, 120mL of vinyl acetate containing azobisisobutyronitrile and 10g of hexene (the molar ratio of the vinyl acetate to the hexene is 10:1) into a reaction container under the stirring condition, pressurizing ethylene to the reaction pressure of 2.5MPa, closing ethylene gas inlet after the reaction is carried out for 6 hours, closing a valve after the reaction is stopped to remove the ethylene pressure, reducing the rotating speed, injecting 5mL of ethanol solution of hydroquinone with the mass fraction of 10%, and then reducing the temperature to below 10 ℃; s4: taking out the obtained reaction product, stirring at normal temperature, and then carrying out the steps of precipitation washing, press drying and vacuum drying at 80 ℃ to obtain the catalyst.
Based on the weight of the EVA material, the EVA material and 2% of foaming agent (AC, aladin, 97% purity) are mixed on an open mill, the mixing temperature is 65 ℃, then the mixed pre-foaming material is transferred into a foaming mold, the foaming temperature is 180 ℃, the pressure is 12MPa, and the EVA foaming material is prepared after heat preservation for 7 min.
Example 2
The specific implementation of this example is the same as example 1, except that: the ternary polymerization EVA elastomer comprises the following 3 structural formula units:
wherein m, n and o are respectively the mole numbers of the formula 1,2 and 4 in the ternary polymerization EVA elastomer, and the mole ratio of m, n and o is 10:3:1.
example 3
The specific implementation of this example is the same as example 1, except that: the reaction pressure in step S3 was 3.5MPa.
Example 4
The specific implementation of this example is the same as example 1, except that: the reaction pressure in step S3 was 4MPa.
Comparative example
EVA1, EVA2, EVA3, EVA4 (except for different reaction time, 0.5h, 1.5h, 2.5h, 3.5h respectively, the rest is the same as the preparation method of the above embodiment 1,2,3, 4), and the preparation of the foaming materials is the same as the preparation method of the embodiment, so as to prepare EVA foaming materials 1,2,3, 4 respectively.
Evaluation of Performance
Rebound resilience: reference is made to GB/T10652-2001 "determination of elasticity of porous elastic materials of high polymers"; compression set: referring to GB/T10653-2001 "determination of compression set of porous elastic Polymer materials", 10 samples were tested for each comparative example, and the average of the values obtained are reported in Table 1.
Tensile strength and elongation at break: referring to GB/T10654-2001 "determination of tensile Strength and elongation at break of Polymer cellular elastic Material", 10 samples were tested for each comparative example, and the average of the values obtained are reported in Table 1.
Claims (10)
1. A ternary copolymer EVA elastomer, characterized in that: the ternary polymerization EVA elastomer at least comprises the following 2 structural formula units:
the ternary polymerization EVA elastomer also comprises any one of the following 2 structural formula units:
wherein m, n and o are respectively the mole numbers of the ternary polymerization EVA elastomer in the formula 1,2,3 or the formula 1,2, 4.
2. The ternary copolymer EVA elastomer of claim 1, wherein: the molar ratio of m to n to o is 0.1-500: 0.1 to 100:0.1 to 100.
3. The ternary copolymer EVA elastomer of claim 2, wherein: the molar ratio of m to n to o is 1-10: 1 to 10:0.1 to 1.
4. A process for the preparation of a ternary copolymer EVA elastomer according to any one of claims 1 to 3, characterized in that: the method comprises the following steps: s1: dissolving an initiator in the vinyl acetate subjected to the water removal treatment for later use; s2: sealing and heating the reaction vessel to 90-110 ℃, pumping and replacing nitrogen atmosphere for three times, vacuumizing and maintaining pressure for 10-12 hours, then heating to 90-110 ℃ in vacuum, filling nitrogen atmosphere, vacuumizing again, repeating for 2-4 times, finally filling ethylene to completely replace nitrogen, and cooling to the reaction temperature; s3: adding solvent, vinyl acetate containing initiator and hexene into a reaction container under stirring, pressurizing nitrogen to reaction pressure, closing ethylene gas inlet after reacting for a period of time, closing a valve to remove ethylene pressure after stopping reacting, reducing rotating speed, injecting a quenching agent, and cooling to below 10 ℃; s4: taking out the obtained reaction product, stirring at normal temperature, and then carrying out the steps of precipitation washing, press drying and vacuum drying.
5. The method for producing a ternary polymerization EVA elastomer according to claim 4, wherein: the reaction temperature in the step S3 is 60-80 ℃; the reaction pressure is 0.1-10 MPa; the reaction time is 4-6 h.
6. The method for producing a ternary polymerization EVA elastomer according to claim 5, wherein: the quenching agent is ethanol solution of hydroquinone, and the volume ratio of the addition amount to the solvent is 1-1.5: 40-80.
7. The method for preparing the ternary polymerization EVA elastomer according to claim 6, wherein the method comprises the following steps: the solvent is any one of C1-C6 alcohol solvent, saturated aliphatic solvent, halohydrocarbon solvent, cycloparaffin solvent, aromatic hydrocarbon solvent, ester solvent, ketone solvent, aldehyde solvent and furan solvent.
8. The method for preparing the ternary polymerization EVA elastomer according to claim 7, wherein the method comprises the following steps: the initiator is at least one of azo initiator and peroxidation initiator.
9. The method for preparing the ternary polymerization EVA elastomer according to claim 8, wherein the method comprises the following steps: the initiator is added with 0.1-10% of material by mass.
10. Use of a ternary copolymer EVA elastomer according to any one of claims 1 to 3, characterized in that: comprises the application of the ternary polymerization EVA elastomer in the fields of shoe wear, plastic toughening and packaging.
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