CN105622817A - Method for preparing EVA/graphene composite material by virtue of in-situ bulk polymerization - Google Patents
Method for preparing EVA/graphene composite material by virtue of in-situ bulk polymerization Download PDFInfo
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- CN105622817A CN105622817A CN201610049858.6A CN201610049858A CN105622817A CN 105622817 A CN105622817 A CN 105622817A CN 201610049858 A CN201610049858 A CN 201610049858A CN 105622817 A CN105622817 A CN 105622817A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 238000012662 bulk polymerization Methods 0.000 title abstract 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229940117958 vinyl acetate Drugs 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical group CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000007306 functionalization reaction Methods 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 150000001451 organic peroxides Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- MWICEJNAECYTMS-UHFFFAOYSA-N [3-(2,4-dimethyl-3-phenylpentan-3-yl)peroxy-2,4-dimethylpentan-3-yl]benzene Chemical group C(C)(C)C(C1=CC=CC=C1)(C(C)C)OOC(C1=CC=CC=C1)(C(C)C)C(C)C MWICEJNAECYTMS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 55
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 55
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000002127 nanobelt Substances 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 graphite alkene Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the technical field of a nano composite material, and in particular relates to a method for preparing an EVA/graphene composite material by virtue of in-situ bulk polymerization. The method comprises the steps: performing the bulk polymerization for ethylene, vinyl acetate, graphene, an initiator and a molecular weight adjusting agent according to a given ratio, thereby obtaining the EVA/graphene composite material. The method is simple in process flow, less in investment, continuous in production, easy to implement and suitable for industrialized production. Graphene in the obtained composite material is uniformly dispersed. The heat stability, mechanical performance and electrical performance of the composite material are remarkably improved; and the economic value is remarkable, and a novel way is provided for the graphene modified EVA material.
Description
Technical field
The invention belongs to Nano-composite materials technical field, be specifically related to a kind of method that body in-situ polymerization prepares EVA/ graphene composite material.
Background technology
Ethylene-vinyl acetate copolymer (EVA), is a kind of by the random copolymer of ethylene and the highly-branched degree of vinylacetate (VAc) two kinds of monomer copolymerizations. EVA is one of topmost ethylene derivative copolymer, can be divided into EVA resin, EVA elastomer and EVA emulsion three major types according to the content difference of VAc in copolymer. EVA has excellent elasticity, pliability, resistance to impact, the filler compatibility and heat sealability, and there is good stress cracking resistance, lower temperature resistance, chemical stability and the feature such as nontoxic so that it is it is widely used in the fields such as film article, expanded material, electric wire, shoemaking, photovoltaic cell packaging adhesive film and PUR.
Along with developing rapidly of nanoscale science and technology, many inorganic nano materials have been assigned the performance of uniqueness, utilize it that polymer is modified, can significantly improve the performances such as the strength of materials, toughness, heat stability, widen the material application in each field.
Graphene is the inorganic nano material that a kind of mechanics, electric property are all very excellent, and its Young's modulus at normal temperatures is up to 1.0TPa, and fracture strength is up to 130GPa, and heat conductivity is up to 5300W/m K, and electron mobility is more than 1500cm2/ V s, resistivity is about 10-8�� m, these special performances become the desirable nanoscale fillers of polymer modification. Research proves, after Graphene is dispersed in polymeric substrate, will can increase substantially the mechanics of polymeric substrate, electrically and thermally performance.
At present, blended method is adopted about the preparation method majority of EVA/ graphene composite material. Ethylene-vinyl acetate copolymer, Graphene powder, white oil, antioxidant, zinc stearate are passed through to mix by Wen Peng etc., plasticizing, pelletize, dehydration, dry, it is prepared for the polyolefin height semiconductive shieldin material (being the Chinese invention patent application of CN103739929A see publication number) of a kind of cable graphene-containing. The tetrahydrofuran solution of vinyl-vinyl acetate copolymer is added drop-wise in the oxolane dispersion liquid of graphene oxide by Xing Yan etc., it is mixed to get the composite of vinyl-vinyl acetate copolymer and graphene oxide, remove solvent, add vulcanizing agent, further mix homogeneously on double; two rollers, at 170 DEG C, emboss sulfidization molding, obtain a kind of vinyl-vinyl acetate copolymer/graphene oxide composite material (Chinese invention patent application see publication number CN102532673B). The graphene suspension being pre-dispersed in chloroformic solution is joined in the chloroformic solution of EVA by Xu Da, under mechanical agitation and ultrasonic combined effect, prepare EVA/ graphene composite material (permitted to reach. the preparation of Graphene and composite polyolefine material thereof and performance study [D]. Harbin University of Science and Technology master thesis .2012.). Zheng Yuying adopts longitudinal oxygen cutting multi-walled carbon nano-tubes legal system to obtain stannic oxide/graphene nano band, Silane coupling reagent KH-570 is utilized to be modified obtaining functional graphene oxide nano belt to it, with EVA resin for matrix, by solution be applied as membrane process obtain functional graphene oxide nano belt/EVA composite material film (Zheng Yuying. the preparation of functional graphene oxide nano belt/EVA composite material film and characterize [J]. material engineering, 2015, (43) 2,96-102.). Zheng Yuying etc. are also by this functional graphene oxide nano belt/EVA composite material film application patent of invention (Chinese invention patent application see publication number CN104212053A). The xylene solution of Graphene is joined in the xylene solution of EVA by Xiao Shujuan etc., mechanical agitation and ultrasonic vibration, obtain EVA/ graphene composite material (Xiao Shujuan, Yu Shouwu, the preparation of Tan's little credit .EVA/ graphene composite material and performance study [J]. chemistry world, 2015,8,501-505.). It is said that in general, employing solution blended process, needing to use substantial amounts of solvent in preparation process, environmental pollution is more serious, and process energy consumption is high, and course of reaction is long, and yield is relatively low, it is virtually impossible to realize industrialization; Adopting melt-blending process, Graphene is difficult to reach the dispersion of nanoscale. And Hu Shengfei by EVA, graphite and other auxiliary agents through twin-screw extrusion pelletizing, obtain the little particle of EVA/ graphite, then blasting stripping method is utilized to prepare resin/graphite alkene conductive plastics foaming concentrate, resin/graphite alkene Conductive plastic masterbatch (being the Chinese invention patent application of CN104592620A see publication number) is obtained then through twin-screw extrusion deaeration, but theory of blasting also immaturity, may cause some to endanger because blasting technique controls unreasonable in preparation process at present.
Up to now, have no the report adopting body situ aggregation method to prepare EVA/ graphene composite material, as fully visible, utilize graphene in-situ modified EVA material can open a new path for EVA/ graphene composite material.
Summary of the invention
The technical problem to be solved is for the deficiencies in the prior art and defect, it is provided that a kind of method that body in-situ polymerization prepares EVA/ graphene composite material. The present invention can make Graphene be uniformly dispersed in EVA base material by in-situ polymerization mode, keeps its nano-meter characteristic, thus obtaining the EVA/ graphene composite material of excellent performance.
To achieve these goals, the solution of the present invention is:
A kind of method that body in-situ polymerization prepares EVA/ graphene composite material, concretely comprises the following steps:
(1) by ethylene, vinylacetate, Graphene, initiator and molecular weight regulator, add in polymeric kettle through compressor by proportioning, under 200 ~ 220 DEG C and 150 ~ 180MPa pressure, carry out polyreaction; (2) reaction terminate after, polymer is separated, extrusion, pelletizing, dry to obtain EVA/ graphene composite material.
Described composition of raw materials is: ethylene 60 ~ 95 parts, vinylacetate 5 ~ 40 parts, Graphene 0.01 ~ 10 part, initiator 0.01 ~ 0.5 part, molecular weight regulator 0.01 ~ 0.1 part.
In described EVA/ graphene composite material, vinylacetate weight percentage is 15 ~ 30%.
Described Graphene is graphene oxide, Graphene, functionalization graphene.
Described functionalization graphene, it is preferable that can finely disseminated functionalization graphene in a solvent, be specially grafted polar group such as hydroxyl, carboxyl, amino, sulfonic group, sulfydryl, fluorin radical, cl radical, bromine group; It is preferred that grafting carbon-carbon double bonds trim.
Described initiator is organic peroxide; Described organic peroxide be tertiary butyl cumyl peroxide, diisopropylbenzyl peroxide, 1,4-dual-tert-butyl peroxy isopropyl base benzene, 2,5-dimethyl-2, double; two (tert-butyl peroxide) hexane of 5-, 2, one or more in double; two (tert-butyl peroxide) hexin of 5-dimethyl-2,5-.
Described molecular weight regulator is mercaptan and derivant thereof, it is preferable that one or more in the mercaptan primary, secondary, tertiary of C5 ~ C14, mercaptan ester, mercaptan ether.
At present, adopting body situ aggregation method to prepare EVA/ graphene composite material and have no report, therefore this patent is that Graphene modified EVA material opens a new path. And adopt composite prepared by this method to have the characteristics that and beneficial effect: (1) adds Graphene in EVA polymerization process, the feature that monomer viscosity is less can be utilized, degree of mixing between the abundant reinforcing material of energy, thus preparing the composite that performance is homogeneous, simultaneously, in-situ polymerization is carried out when Graphene participates in, matrix can form good interface with Graphene, increase the switching performance at the two interface, and then the overall performance of raising composite, and prepare the composite of excellent performance; (2) the method have that technological process is simple, small investment, environmental friendliness, production can the advantage such as serialization, possess the probability of industrialized production.
Detailed description of the invention
In order to be better understood from the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but present invention is not limited solely to the following examples.
Embodiment 1
Carry out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, graphene powder 0.1 part, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Embodiment 2
Carry out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, graphene powder 0.2 part, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Embodiment 3
Carry out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, graphene powder 0.5 part, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Embodiment 4
Carrying out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, graphene powder 1 part, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Embodiment 5
Carrying out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, graphene powder 2 parts, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Embodiment 6
Carry out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, graphene oxide 0.5 part, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, graphene oxide, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Embodiment 7
Carry out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, functionalization graphene 0.5 part, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Functionalization graphene is to carry out silane coupled at 60 DEG C with ��-aminopropyl triethoxysilane, and wherein ��-aminopropyl triethoxysilane is 0.03:1 with the weight ratio of Graphene.
Ethylene, vinylacetate, functionalization graphene, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA/ graphene composite material.
Comparative example
Carrying out body in-situ polymerization according to formula as below and prepare EVA/ graphene composite material: ethylene is 60 parts, vinylacetate 40 parts, tertiary butyl cumyl peroxide 0.1 part, n-dodecyl mercaptan 0.05 part, mark weighs by weight.
Ethylene, vinylacetate, tertiary butyl cumyl peroxide, n-dodecyl mercaptan mixing and stirring are added in polymeric kettle through compressor, it is warming up to 220 DEG C, polyreaction is carried out under 180MPa, after reaction terminates, first the copolymer of acquisition is separated in the high-pressure separator of 25MPa with unreacted gas, unreacted gas participates in reaction again through high-pressure recycle system, and polymer is separated from low pressure separator, extruded, pelletizing, dry obtains EVA resin.
Above-mentioned comparative example is that the substance law without Graphene prepares EVA resin. Embodiment 15, when other conditions are constant, investigates the different Graphene addition impact (being listed in table 1) on EVA resin hot strength. Embodiment 3,6,7 has investigated interpolation Graphene, graphene oxide, the functionalization graphene impact (being listed in table 2) on EVA resin stretching resin.
The composite hot strength contrast of the different Graphene content of table 1
| Embodiment | Graphene addition (part) | Hot strength (MPa) |
| Comparative example | 0 | 10.8 |
| Embodiment 1 | 0.1 | 19.5 |
| Embodiment 2 | 0.2 | 22.4 |
| Embodiment 3 | 0.5 | 29.3 |
| Embodiment 4 | 1 | 22.1 |
| Embodiment 5 | 2 | 20.9 |
The hot strength contrast of the composite of the different Graphene of table 2
| Embodiment | Different Graphenes | Hot strength (MPa) |
| Comparative example | Without Graphene | 10.8 |
| Embodiment 3 | Graphene powder | 29.3 |
| Embodiment 6 | Graphene oxide | 31.6 |
| Embodiment 7 | Functionalization graphene | 36.5 |
As can be seen from Table 1, the hot strength of EVA/ graphene composite material weakens afterwards along with the increase of Graphene addition first strengthens, and when Graphene addition is 0.5 part, the hot strength of composite reaches maximum. As can be seen from Table 2, the tensile strength performance of composite is promoted obvious gradually by Graphene, graphene oxide, functionalization graphene.
To sum up illustrating that the hot strength to EVA material of adding of Graphene has lifting effect, functionalization graphene can have the good compatibility with polymeric matrix, becomes apparent from than the lifting of graphene oxide and Graphene.
Selected embodiment is typical embodiments above, and described above is only intended to help to understand method and the core concept thereof of the present invention. It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (4)
1. the method that a body in-situ polymerization prepares EVA/ graphene composite material, concretely comprise the following steps: (1) is by ethylene, vinylacetate, Graphene, initiator and molecular weight regulator, add in polymeric kettle through compressor by proportioning, under 200 ~ 220 DEG C and 150 ~ 180MPa pressure, carry out polyreaction; (2) reaction terminate after, polymer is separated, extrusion, pelletizing, dry to obtain EVA/ graphene composite material;
Described composition of raw materials is ethylene 60 ~ 95 parts, vinylacetate 5 ~ 40 parts, Graphene 0.01 ~ 10 part, initiator 0.01 ~ 0.5 part, molecular weight regulator 0.01 ~ 0.1 part.
2. the method that a kind of body in-situ polymerization as claimed in claim 1 prepares EVA/ graphene composite material, it is characterised in that in described EVA/ graphene composite material, vinylacetate weight percentage is 15 ~ 30%.
3. the method that a kind of body in-situ polymerization as claimed in claim 1 prepares EVA/ graphene composite material, it is characterised in that described Graphene is graphene oxide, Graphene, functionalization graphene.
4. the method that a kind of body in-situ polymerization as claimed in claim 1 prepares EVA/ graphene composite material, it is characterised in that described initiator is organic peroxide; Described organic peroxide be tertiary butyl cumyl peroxide, diisopropylbenzyl peroxide, 1,4-dual-tert-butyl peroxy isopropyl base benzene, 2,5-dimethyl-2, double; two (tert-butyl peroxide) hexane of 5-, 2, one or more in double; two (tert-butyl peroxide) hexin of 5-dimethyl-2,5-.
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