CN105622817B - The method that body in-situ polymerization prepares EVA/ graphene composite materials - Google Patents
The method that body in-situ polymerization prepares EVA/ graphene composite materials Download PDFInfo
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- CN105622817B CN105622817B CN201610049858.6A CN201610049858A CN105622817B CN 105622817 B CN105622817 B CN 105622817B CN 201610049858 A CN201610049858 A CN 201610049858A CN 105622817 B CN105622817 B CN 105622817B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 107
- 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 20
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940117958 vinyl acetate Drugs 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000006243 chemical 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims 2
- QLVHFTGKDGTJDH-UHFFFAOYSA-N acetic acid;ethenyl acetate Chemical compound CC(O)=O.CC(=O)OC=C QLVHFTGKDGTJDH-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 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
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 54
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- -1 graphite alkene Chemical class 0.000 description 11
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 239000004575 stone Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 238000003756 stirring 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
- 238000002156 mixing Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002127 nanobelt 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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000945 filler Substances 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
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 206010036590 Premature baby Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Chemical group 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- MSAVICZWFPQFPO-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.C=C.CC(O)=O MSAVICZWFPQFPO-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000006185 dispersion Substances 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
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002240 furans Chemical class 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
- 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000004080 punching Methods 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
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000008096 xylene Substances 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
-
- 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 nano composite material preparing technical field, and in particular to a kind of method that body in-situ polymerization prepares EVA/ graphene composite materials.Ethene, vinylacetate, graphene, initiator, molecular weight regulator are carried out polymerisation in bulk by the method according to a certain ratio, obtain EVA/ graphene composite materials.The method technological process is simple, small investment, production can serialization, easily implement, it is adapted to industrialized production, graphene uniform disperses in the composite of gained, the heat endurance of composite, mechanics, electric property are obviously improved, it is that graphene modified EVA material opens a new way with considerable economic value.
Description
Technical field
The invention belongs to nano composite material preparing technical field, and in particular to a kind of body in-situ polymerization prepares EVA/ stones
The method of black alkene composite.
Background technology
Ethylene-vinyl acetate copolymer（EVA）, be one kind by ethene and vinylacetate（VAc）Two kinds of monomer copolymerizations
Highly -branched degree random copolymer.EVA is one of topmost ethylene derivative copolymer, according to VAc in copolymer
Content difference can be divided into EVA resin, EVA elastomers and EVA emulsion three major types.EVA has excellent elasticity, pliability, resistance to punching
Hitting property, filler compatibility and heat sealability, and with good stress cracking resistance, lower temperature resistance, chemical stability and nontoxic
The features such as, it is widely used in film article, expanded material, electric wire, shoemaking, photovoltaic cell packaging adhesive film and heat
The fields such as melten gel.
With developing rapidly for nanoscale science and technology, many inorganic nano materials have been assigned the performance of uniqueness, utilize it
Polymer is modified, the performances such as the strength of materials, toughness, heat endurance can be significantly improved, material answering in each field is widened
With.
Graphene is a kind of mechanics, electric property all very excellent inorganic nano materials, its Young's modulus at normal temperatures
Up to 1.0TPa, fracture strength is up to 130GPa, and thermal conductivity factor is up to 5300W/mK, and electron mobility is more than 1500cm2/
Vs, resistivity is about 10-8Ω m, these special performances become the preferable nanoscale fillers of polymer modification.Grind
Study carefully proof, after graphene is dispersed in polymeric substrate, will can increase substantially mechanics, the electricity of polymeric substrate
And thermal property.
At present, the method for using blending about the preparation method majority of EVA/ graphene composite materials.Warm roc etc. by ethene-
Acetate ethylene copolymer, Graphene powder, white oil, antioxidant, zinc stearate are plastified by mixing, are granulated, and are dehydrated, and are dried, system
For a kind of high semiconductive shieldin material of polyolefin of cable graphene-containing（See Publication No. CN103739929 A middle promulgated by the State Council
Bright patent application）.The tetrahydrofuran solution of vinyl-vinyl acetate copolymer is added drop-wise to the tetrahydrochysene of graphene oxide by Xing Yan etc.
In furans dispersion liquid, the composite of vinyl-vinyl acetate copolymer and graphene oxide is mixed to get, solvent is removed, plus
Enter vulcanizing agent, be further well mixed in double roller, sulfidization molding is molded at 170 DEG C, obtain a kind of ethane-acetic acid ethyenyl ester
Copolymer/graphene oxide composite material（See publication number CN102532673 B Chinese invention patent application）.Xu Da will be advance
The graphene suspension being dispersed in chloroformic solution is added in EVA chloroformic solution, in the common work of mechanical agitation and ultrasound
Under, EVA/ graphene composite materials are prepared（Perhaps up to graphenes and its preparation and the performance study of composite polyolefine material
[D] Harbin University of Science and Technologys master thesis .2012.）.Zheng Yuying is using longitudinal direction oxidation cutting multi-walled carbon nanotube legal system
Stannic oxide/graphene nano band is obtained, it is modified using Silane coupling reagent KH-570 and obtains functional graphene oxide nanometer
Band, using EVA resin as matrix, coats film-forming process by solution and obtains functional graphene oxide nanobelt/EVA composites
Film（The preparation of Zheng Yu baby functional graphene oxides nanobelt/EVA composite material films and sign [J] material engineering,
2015,(43)2,96-102.）.Zheng Yuying etc. is also by the functional graphene oxide nanobelt/EVA composite material film applications
Patent of invention（See publication number CN104212053 A Chinese invention patent application）.Xiao Shujuan etc. is by the dimethylbenzene of graphene
Solution is added in EVA xylene solution, mechanical agitation and ultrasonic vibration, obtains EVA/ graphene composite materials（Xiao Shujuan,
Yu Shouwu, the preparation of the small credit .EVA/ graphene composite materials of Tan and performance study [J] chemistry worlds, 2015,8,501-
505.）.In general, using solution blended process, needing to use substantial amounts of solvent in preparation process, environmental pollution is tighter
Weight, and process energy consumption is high, course of reaction is long, and yield is relatively low, it is virtually impossible to realize industrialization；Using melt-blending process, graphene
It is difficult to reach the scattered of nanoscale.And Hu Shengfei by EVA, graphite and other auxiliary agents through twin-screw extrusion pelletizing, obtain
EVA/ graphite small particles, then prepare resin/graphite alkene conductive plastics foaming concentrate, then squeeze through twin-screw using blasting stripping method
Go out deaeration and obtain resin/graphite alkene Conductive plastic masterbatch（See the A of Publication No. CN 104592620 Chinese invention patent Shen
Please）, but theory of blasting also prematurity at present, in preparation process may because blasting technique control is unreasonable and caused by some endanger
Evil.
So far, the report that EVA/ graphene composite materials are prepared using body situ aggregation method is had no, as fully visible,
A new path can be opened using graphene in-situ modified EVA material for EVA/ graphene composite materials.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of body original position is poly- with defect in view of the shortcomings of the prior art
Close the method for preparing EVA/ graphene composite materials.The present invention can make graphene in EVA base materials by in-situ polymerization mode
In be uniformly dispersed, its nano-meter characteristic is kept, so as to obtain the EVA/ graphene composite materials of excellent performance.
To achieve these goals, solution of the invention is：
A kind of method that body in-situ polymerization prepares EVA/ graphene composite materials, is concretely comprised the following steps：
（1）By ethene, vinylacetate, graphene, initiator and molecular weight regulator, added by proportioning through compressor poly-
Close in kettle, in carrying out polymerisation under 200 ~ 220 DEG C and 150 ~ 180MPa pressure；（2）Reaction terminate after, polymer through separation,
Extrusion, pelletizing, dry EVA/ graphene composite materials.
The composition of raw materials is：60 ~ 95 parts of ethene, 5 ~ 40 parts of vinylacetate, 0.01 ~ 10 part of graphene, initiator
0.01 ~ 0.5 part, 0.01 ~ 0.1 part of molecular weight regulator.
Vinylacetate weight percentage is 15 ~ 30% in the EVA/ graphene composite materials.
The graphene is graphene oxide, graphene, functionalization graphene.
The functionalization graphene, it is preferable that can well dispersed functionalization graphene in a solvent, be specially grafted pole
Property group such as hydroxyl, carboxyl, amino, sulfonic group, sulfydryl, fluorin radical, cl radical, bromine group；Further preferably it is grafted carbon containing carbon
Double bond trim.
The initiator is organic peroxide；The organic peroxide is tertiary butyl cumyl peroxide, two
Cumyl peroxide, 1,4 bis tert butyl peroxy isopropyl benzene, 2,5- dimethyl -2,5- are double（Tert-butyl peroxide）Oneself
Alkane, 2,5- dimethyl -2,5- are double（Tert-butyl peroxide）One or more in hexin.
The molecular weight regulator is mercaptan and its derivative, it is preferable that C5 ~ C14 primary, secondary, tertiary mercaptan, mercaptan ester, sulphur
One or more in alcohol ether.
At present, EVA/ graphene composite materials are prepared using body situ aggregation method and has no report, therefore this patent is stone
Black alkene modified EVA material opens a new path.And the composite prepared using the method is had the characteristics that and beneficial
Effect：（1）Add graphene in EVA polymerization processes, it is possible to use the less feature of monomer viscosity, can fully reinforcing material it
Between degree of mixing, so as to prepare the homogeneous composite of performance, meanwhile, carried out in the case where graphene is participated in situ poly-
Close, matrix can form good interface, the switching performance at the two interface of increase with graphene, and then improve the whole of composite
Body performance, and prepare the composite of excellent performance；（2）This method has that technological process is simple, small investment, environment friend
Good, production can serialization the advantages of, possess the possibility of industrialized production.
Embodiment
In order to be better understood from the present invention, with reference in the embodiment content that the present invention is furture elucidated, but the present invention
Appearance is not limited solely to the following examples.
Embodiment 1
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 0.1 part of graphene powder, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan is pressed
Weight fraction is weighed.
Ethene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan are mixed
Conjunction stirs to be added in polymeric kettle through compressor, is warming up to 220 DEG C, and polymerisation is carried out under 180MPa, after reaction terminates,
The copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through high pressure
The circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/ stones
Black alkene composite.
Embodiment 2
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 0.2 part of graphene powder, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan is pressed
Weight fraction is weighed.
Ethene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan are mixed
Conjunction stirs to be added in polymeric kettle through compressor, is warming up to 220 DEG C, and polymerisation is carried out under 180MPa, after reaction terminates,
The copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through high pressure
The circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/ stones
Black alkene composite.
Embodiment 3
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 0.5 part of graphene powder, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan is pressed
Weight fraction is weighed.
Ethene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan are mixed
Conjunction stirs to be added in polymeric kettle through compressor, is warming up to 220 DEG C, and polymerisation is carried out under 180MPa, after reaction terminates,
The copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through high pressure
The circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/ stones
Black alkene composite.
Embodiment 4
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 1 part of graphene powder, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan, by weight
Fraction is measured to weigh.
Ethene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan are mixed
Conjunction stirs to be added in polymeric kettle through compressor, is warming up to 220 DEG C, and polymerisation is carried out under 180MPa, after reaction terminates,
The copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through high pressure
The circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/ stones
Black alkene composite.
Embodiment 5
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 2 parts of graphene powder, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan, by weight
Fraction is measured to weigh.
Ethene, vinylacetate, graphene powder, tertiary butyl cumyl peroxide, n-dodecyl mercaptan are mixed
Conjunction stirs to be added in polymeric kettle through compressor, is warming up to 220 DEG C, and polymerisation is carried out under 180MPa, after reaction terminates,
The copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through high pressure
The circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/ stones
Black alkene composite.
Embodiment 6
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 0.5 part of graphene oxide, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan is pressed
Weight fraction is weighed.
Ethene, vinylacetate, graphene oxide, tertiary butyl cumyl peroxide, n-dodecyl mercaptan are mixed
Conjunction stirs to be added in polymeric kettle through compressor, is warming up to 220 DEG C, and polymerisation is carried out under 180MPa, after reaction terminates,
The copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through high pressure
The circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/ stones
Black alkene composite.
Embodiment 7
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 0.5 part of functionalization graphene, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan,
Fraction by weight is weighed.
Functionalization graphene is that silane coupled, wherein γ-ammonia is carried out at 60 DEG C with γ-aminopropyl triethoxysilane
The weight ratio of propyl-triethoxysilicane and graphene is 0.03:1.
By ethene, vinylacetate, functionalization graphene, tertiary butyl cumyl peroxide, n-dodecyl mercaptan
It is mixed evenly and is added through compressor in polymeric kettle, is warming up to 220 DEG C, polymerisation is carried out under 180MPa, reaction terminates
Afterwards, the copolymer of acquisition is separated with unreacted gas in 25MPa high-pressure separator first, unreacted gas is through height
The pressure circulatory system participates in reaction again, and polymer is separated from low pressure separator, extruded, pelletizing, is dried to obtain EVA/
Graphene composite material.
Comparative example
Body in-situ polymerization is carried out according to formula as below and prepares EVA/ graphene composite materials：Ethene is 60 parts, acetic acid second
40 parts of alkene ester, 0.1 part of tertiary butyl cumyl peroxide, 0.05 part of n-dodecyl mercaptan, by weight fraction are weighed.
By ethene, vinylacetate, tertiary butyl cumyl peroxide, n-dodecyl mercaptan be mixed evenly through
Compressor is added in polymeric kettle, is warming up to 220 DEG C, polymerisation is carried out under 180MPa, after reaction terminates, first by acquisition
Copolymer is separated with unreacted gas in 25MPa high-pressure separator, unreacted gas through high-pressure recycle system again
Reaction is participated in, polymer separates from low pressure separator, extruded, pelletizing, be dried to obtain EVA resin.
Above-mentioned comparative example is the substance law preparation EVA resin without graphene.Embodiment 1-5 is constant in other conditions
In the case of, investigate influence of the different graphene additions to EVA resin tensile strength（It is listed in Table 1 below）.Embodiment 3,6,7 is examined
The influence of addition graphene, graphene oxide, functionalization graphene to EVA resin stretching resin is examined（It is listed in Table 2 below）.
The composite tensile strength contrast of the different graphene contents of table 1
| Embodiment | Graphene addition（Part） | Tensile 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 tensile strength contrast of the composite of the different graphenes of table 2
| Embodiment | Different graphenes | Tensile 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 tensile strength of EVA/ graphene composite materials is with the increase of graphene addition
First strengthen and weaken afterwards, when graphene addition is 0.5 part, the tensile strength of composite reaches maximum.Can be with from the data of table 2
Find out, the tensile strength performance lifting of graphene, graphene oxide, functionalization graphene to composite is gradually obvious.
To sum up illustrating the addition of graphene has lifting effect to the tensile strength of EVA material, and functionalization graphene can be with gathering
Compound matrix has good compatibility, and the lifting than graphene oxide and graphene becomes apparent from.
Selected embodiment is typical embodiments above, and described above is only intended to the method for helping to understand the present invention
And its core concept.It should be pointed out that for those skilled in the art, before the principle of the invention is not departed from
Put, some improvement and modification can also be carried out to the present invention, these are improved and modification also falls into the guarantor of the claims in the present invention
In the range of shield.
Claims (4)
1. a kind of method that body in-situ polymerization prepares EVA/ graphene composite materials, is concretely comprised the following steps：（1）By ethene, acetic acid
Vinyl acetate, graphene, initiator and molecular weight regulator, are added in polymeric kettle by proportioning through compressor, in 200 ~ 220 DEG C and
Polymerisation is carried out under 150 ~ 180MPa pressure；（2）After reaction terminates, polymer is through separation, extrusion, pelletizing, dry EVA/
Graphene composite material；
The composition of raw materials is 60 ~ 95 parts of ethene, 5 ~ 40 parts of vinylacetate, 0.01 ~ 10 part of graphene, initiator 0.01 ~ 0.5
Part, 0.01 ~ 0.1 part of molecular weight regulator.
2. the method that a kind of body in-situ polymerization as claimed in claim 1 prepares EVA/ graphene composite materials, its feature exists
Vinylacetate weight percentage is 15 ~ 30% in the EVA/ graphene composite materials.
3. the method that a kind of body in-situ polymerization as claimed in claim 1 prepares EVA/ graphene composite materials, its feature exists
Graphene oxide, functionalization graphene are could alternatively be in the graphene.
4. the method that a kind of body in-situ polymerization as claimed in claim 1 prepares EVA/ graphene composite materials, its feature exists
In the initiator be organic peroxide；The organic peroxide is tertiary butyl cumyl peroxide, diisopropylbenzene (DIPB)
Base peroxide, 1,4 bis tert butyl peroxy isopropyl benzene, 2,5- dimethyl -2,5- are double（Tert-butyl peroxide）Hexane, 2,5-
Dimethyl -2,5- is double（Tert-butyl peroxide）One or more in hexin.
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| CN104087211A (en) * | 2014-07-29 | 2014-10-08 | 南京航空航天大学 | Adhesive for anticorrosive paint for deep-sea oil-gas delivery steel tube outer walls and preparation method thereof |
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| CN105085835A (en) * | 2014-05-14 | 2015-11-25 | 泰山玻璃纤维有限公司 | Graphene modified polyvinyl acetate film forming agent preparation method |
| EP2960274A1 (en) * | 2014-06-23 | 2015-12-30 | Solvay SA | One pot synthesis of thermally reduced graphene oxide (TRGO)-polymer nanocomposites. |
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