CN107022183A - A kind of preparation method of automobile engineering plastics special graphite alkene masterbatch - Google Patents
A kind of preparation method of automobile engineering plastics special graphite alkene masterbatch Download PDFInfo
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- CN107022183A CN107022183A CN201710353718.2A CN201710353718A CN107022183A CN 107022183 A CN107022183 A CN 107022183A CN 201710353718 A CN201710353718 A CN 201710353718A CN 107022183 A CN107022183 A CN 107022183A
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- graphene
- engineering plastics
- microballoon
- automobile engineering
- graphite alkene
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 53
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 47
- -1 graphite alkene Chemical class 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 36
- 239000010439 graphite Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 138
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 131
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 230000009514 concussion Effects 0.000 claims description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 15
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- 230000003068 static effect Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000001993 wax Substances 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 9
- 238000007667 floating Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000004425 Makrolon Substances 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007998 bicine buffer Substances 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 238000001704 evaporation Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000010355 oscillation Effects 0.000 claims 1
- 239000002096 quantum dot Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005469 granulation Methods 0.000 abstract description 7
- 230000003179 granulation Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000004575 stone Substances 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch, graphene is combined with porous microsphere in advance with slurry form, porous microsphere is set to carry graphene, add Silante terminated base polyurethane prepolymer for use as, it polymerize through high-pressure fog and connects, is then dispersed in granulation in vector resin and obtains graphene masterbatch.The present invention provides the above method and overcomes the scattered technological deficiency that fails effectively improve of the graphene during automobile engineering plastics-production processes use in the prior art, realize well dispersed technique effect in automobile engineering plastics, and then there is the effect of high-strength reduction in automobile engineering plastic applications, it is the critical material of automotive light weight technology.Particularly, the graphene masterbatch has high fluidity because of the presence of high sphericity microballoon, is exclusively used in automobile engineering plastics, effectively overcomes ordinary graphite alkene masterbatch to be difficult to the scattered defect of flowing.The scheme preparation technology of disclosure of the invention is simple, it is easy to accomplish scale industrial production.
Description
Technical field
The present invention relates to grapheme material field, and in particular to a kind of preparation of automobile engineering plastics special graphite alkene masterbatch
Method.
Background technology
With the rise of automotive light weight technology, the use of automobile plastic parts is more and more.Automobile is moulded by developed country
Doses accounts for integral material as an important symbol for weighing Automobile Design and manufacture level height, German automobiles with plastics
15%.China's development of automobile industry is rapid in recent years, and current automobile annual production is more than 4,000,000, with reference to external trend, automobile
Industry year, modified plastics will be more than 500,000 tons, and wherein engineering plastics account for a big chunk ratio, various applied to automobile
Parts.But facing to automobile lighting, high strengthening development trend, the modification of existing engineering plastics has been difficult to meet automobile
The demand of development.
Graphite is dilute be earliest as Univ Manchester UK Andre Geim in 2004 made from.It is to be currently known most
Thin two-dimensional material, its thickness is only 0.335nm, and it is made up of the lattice of six sides.Dilute graphite is considered as fowler coal, carbon nanometer
Pipe, the basic structural unit of graphite, because its mechanics, quantum and electrical properties are special, are paid high attention to by physics and material educational circles.
Graphene is most thin, the most hard nano material in known world, and the dilute stretch modulus of graphite and ultimate strength are received with single armed carbon
Carry out pipe quite, its light weight, thermal conductivity is good and specific surface area is big.Graphene is as a kind of high-performance reinforcing material, as from now on
The first choice of automobile specified plastics.
Because graphene prevents it to exist from what is stablized with form of single sheet in the presence of stronger model ylid bloom action power each other, stone
Black alkene is once reunited stacking, and its thermal conductivity, which occurs, drastically to be declined, and difficult between layers once occurring graphene if layer is stacked
To open, it is necessary to peel off again.Research more at present is the dispersiveness that graphene is improved by dispersant, but due to graphite
Alkene is different from common inorganic particle, and conventional dispersant and scattered means are difficult to reach dispersion effect.But automobile engineering is moulded
Expect usual poor fluidity, graphene dispersion is wherein increasingly difficult.
Chinese Patent Application No. 201310629451.7 discloses a kind of graphene with polymolecularity/carbon black thermoplastic
Property resin concentrates and preparation method thereof, the charging property of graphene is adjusted and by electrostatic self-assembled technology using surface modifier,
Graphene/carbon black hybrid material is prepared, the reunion of graphene in last handling process is effectively prevent, the stone of good dispersion is obtained
Black alkene masterbatch.But the problem of preparing with the dissipation of electric charge is faced in storing process, requires higher to technique continuity.
Chinese Patent Application No. 201510916570.X discloses what a kind of raising graphene disperseed in polymeric matrix
Method, passes through the graft reaction that is induced during melt-processed so that in the masterbatch system of preparation using lewis acid catalyst
Graphenic surface has been grafted long-chain molecule, and the graphene of long-chain grafting is diluted compound tense with polymer by melt-processed,
It can significantly improve graphene in the base scattered.Although this method can suppress the generation of graphene reunion, this
Need to accurately control reaction condition, and use special organic catalyst, working condition is more harsh, is unfavorable for extensive work
Industry metaplasia is produced.
It follows that to improve dispersiveness of the graphene during production and processing use, it is necessary to propose that one kind can have
Effect solves the problem of graphene is easily reunited, and improves uniformly dispersed preparation scheme of the graphene in masterbatch, is further able to
Preferably play the performance of graphene high-strength reduction.Particularly, the usual poor fluidity of automobile engineering plastics, graphene dispersion
It is wherein increasingly difficult.Realize graphene and strengthen in automobile engineering plastics, light-weighted extensive use, primarily solve graphene
High flowing dispersiveness.
The content of the invention
Scattered fail effectively to carry during automobile engineering plastics-production processes use for graphene in the prior art
High technological deficiency, the present invention proposes a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch, by graphene to starch
Body form is compound with porous microsphere in advance, porous microsphere is carried graphene, Silante terminated base polyurethane prepolymer for use as is added, through height
Spray polymerization connection is pressed, granulation in vector resin is then dispersed in and obtains graphene masterbatch.The present invention provides the above method and overcome
The scattered technology that fails effectively improve of the graphene during automobile engineering plastics-production processes use lacks in the prior art
Fall into, realize well dispersed technique effect in automobile engineering plastics, and then with high-strength in automobile engineering plastic applications
The effect of minimizing is spent, is the critical material of automotive light weight technology.Particularly, the graphene masterbatch is because of the presence of high sphericity microballoon
With high fluidity, automobile engineering plastics are exclusively used in, effectively overcome ordinary graphite alkene masterbatch to be difficult to the scattered defect of flowing.Invention
Disclosed scheme preparation technology is simple, it is easy to accomplish scale industrial production.
To solve the above problems, the present invention uses following technical scheme：
A kind of preparation method of automobile engineering plastics special graphite alkene masterbatch, it is characterized in that being carried out by the following raw material according to parts by weight
Prepare：
50-70 parts of graphene slurry；
20-30 parts of vector resin；
10-15 parts of porous microsphere；
5-10 parts of Silante terminated base polyurethane prepolymer for use as；
3-5 parts of modifier；
0.3-1 parts of surfactant；
Specific preparation method is as follows：
（1）By porous microsphere and the uniform progress surface modification of surfactant blending concussion, then to surface modified porous microballoon
Screened, obtain surface modified porous microballoon；
（2）The surface modified porous microballoon is added in pressure vessel, graphene slurry is added, stirs, 10- is stood
30 min, progressively pressurize to pressure vessel, control pressing speed, to static pressure 6-20 MPa, graphene slurry are pressed into porous
In the duct of microballoon, static condition is kept 2-3 hours, make graphene is stable to be attached to channel surfaces；
（3）Graphene composite porous microspheres are passed through conventional filtration by removal pressure, add Silante terminated base polyurethane prepolymer for use as,
It polymerize through high-pressure fog and connects, assembling obtains graphene/porous microsphere composite；
（4）The graphene/porous microsphere composite is scattered in vector resin, modifier is added, stirs,
Automobile engineering plastics special graphite alkene masterbatch is obtained by extruder grain；
Wherein, the mass concentration of the graphene slurry is 10-20%；
The porous microsphere is that particle diameter is 100-250nm, sphericity ＞ 0.85 calcium carbonate microspheres, barium sulfate in 5-12 μm, aperture
At least one of microballoon, floating bead microballoon, hydroxyapatite micro-sphere, alundum (Al2O3) microballoon and silicon dioxide microsphere；
The surfactant is polyamide wax, polypropylene wax, EVA waxes, calcium stearate and magnesium stearate, ethylene group stearic bicine diester
Amine, oleamide, erucyl amide, phthalic acid ester, citrate, lauryl sodium sulfate, dodecyl sodium sulfate and poly-
One or more in vinylpyrrolidone.
The vector resin is at least one in nylon material, polyurethane material, makrolon material, polypropylene material
Kind；
The modifier is epoxidized soybean oil, o-phthalic acid dibutyl ester, dioctyl sebacate, the isodecyl of phthalic acid two
One or more of mixtures of ester.
Because graphene prevents it to exist from what is stablized with form of single sheet in the presence of stronger model ylid bloom action power each other, stone
Black alkene is once reunited stacking, and its thermal conductivity, which occurs, drastically to be declined, and difficult between layers once occurring graphene if layer is stacked
To open, it is necessary to peel off again.Research more at present is the dispersiveness that graphene is improved by dispersant, but due to graphite
Alkene is different from common inorganic particle, and conventional dispersant and scattered means are difficult to reach dispersion effect.But automobile engineering is moulded
Expect usual poor fluidity, graphene dispersion is wherein increasingly difficult.In consideration of it, the present invention proposes one kind, effectively to solve graphene easy
The problem of reunion, improve uniformly dispersed preparation scheme of the graphene in masterbatch, by graphene with slurry form in advance with
High sphericity porous microsphere is combined, and porous microsphere is carried graphene, the Silante terminated base polyurethane prepolymer for use as by adding, through high pressure
Spraying, its significant advantage be Silante terminated base polyurethane prepolymer for use as in porous microsphere surface aggregate, and again under high pressure disperse shape
Into the microballoon fixed one by one by thermoplastic polyurethane film, it has good dispersiveness, further stablizes stone while scattered
Black alkene, prevents it from reuniting.The rolling action of high sphericity microballoon and high fluidity cause graphene high-efficiency to be dispersed in vector resin
Graphene masterbatch is obtained, particularly, the graphene masterbatch has high fluidity because of the presence of high sphericity microballoon, is exclusively used in automobile
Engineering plastics, effectively overcome ordinary graphite alkene masterbatch to be difficult to the scattered defect of flowing.
Although in automobile engineering plastic processing, mobility can be improved by improving the lubricants such as wax, it will be clear that mistake
The use of amount lubricant can have a negative impact to the intensity of engineering plastics.By the present invention in that being carried with high sphericity porous microsphere
Graphene, not only solves the scattering problem of graphene, and cause the masterbatch to have good add in automobile engineering plastics
Work mobility.
A kind of preparation method of automobile engineering plastics special graphite alkene masterbatch of the present invention, compared with prior art, it is protruded
The characteristics of and excellent effect be：
1st, the preparation method for a kind of automobile engineering plastics special graphite alkene masterbatch that the present invention is provided, by graphene with slurry form
It is compound with high sphericity porous microsphere in advance, porous microsphere is carried graphene, Silante terminated base polyurethane prepolymer for use as is added, through height
Spray polymerization connection is pressed, it is firm that this, which is combined, so that high efficiency dispersion obtains graphene masterbatch in vector resin.
2nd, by the present invention in that carrying graphene with high sphericity porous microsphere, the scattering problem of graphene is not only solved,
And cause the masterbatch that there is good processing fluidity in automobile engineering plastics.
3rd, scheme preparation technology disclosed by the invention is simple, it is easy to accomplish scale industrial production.The graphene of offer is female
Material in automobile engineering plastics it is well dispersed be suitable for substitute carbon fiber, glass fibre be used for front/rear collision bumper, automotive trim,
Automobile case, radiator etc., the effect with high-strength reduction is the critical material of automotive light weight technology.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）It it is 10 parts by parts by weight, particle diameter is the calcium carbonate microspheres and 0.3 weight of 250nm, sphericity more than 0.85 in 5 μm, aperture
Measure the blending concussion of part polyamide wax uniform, setting concussion frequency is 10Hz, and then the porous calcium carbonate microballoon that surface is modified is entered
Row conventional centrifugal is screened, and the rotating speed of centrifugation is 300 rpm, removes the broken microballoon of concussion, obtains sphericity intact more than 0.85
Surface modified calcium carbonate microballoon；
（2）Surface modified calcium carbonate microballoon is added in pressure vessel, the graphene slurry that parts by weight are 50 parts is added, its is molten
Agent is water, and mass concentration is 10%, wherein solute graphene be single-layer graphene and multi-layer graphene mixed-powder, powder
Particle diameter is 100nm, and thickness is less than 1.6nm, stirs, and stands 10-30 min, is 0.05 MPa/min to liquid using pressing speed
Plus the MPa of static pressure 20, by the duct of graphene slurry press-in porous calcium carbonate microballoon, keep static condition 2 hours, make stone
Black alkene is stable to be attached to channel surfaces；
（3）Graphene composite porous microspheres are passed through conventional filtration by removal pressure, add the Silante terminated polyurethane of 5 parts by weight
Performed polymer, polymerize through high-pressure fog and connects, and assembling obtains graphene/porous calcium carbonate microballoon composite；
（4）The graphene/porous calcium carbonate microballoon composite is scattered in the nylon material that parts by weight are 20 parts, added
5 parts by weight epoxy soybean oils, are stirred, and automobile engineering plastics special graphite alkene is obtained by double screw extruder extruder grain
Masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment is obtained prepares vapour with 5% mass ratio and 95%ABS blendings
Car bumper, with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch（Directly disperse graphene in vector resin granulation
Arrive）Enhancing performance is compared, and the present embodiment is shown often to be flowed to automobile with the significant enhancement of engineering plastics and good processing
Property.Specific test can be as shown in table 1.
Embodiment 2
（1）It it is 15 parts by parts by weight, particle diameter is in the barium sulfate microballoon and 0.5 weight that 10 μm, aperture are that 250nm sphericitys are more than 0.85
Measure that the blending concussion of part polyamide wax is uniform, it is 35Hz to set concussion frequency, then surface modified porous microballoon is carried out it is conventional from
The heart is screened, and the rotating speed of centrifugation is 130 rpm, removes the broken microballoon of concussion, obtains intact surface modified barium sulphate microballoon；
（2）Surface modified barium sulphate microballoon is added in pressure vessel, the graphene slurry that parts by weight are 60, its solvent is added
The graphene slurry for being 15% for water, Solute mass concentration, wherein solute graphene are redox graphene powder, powder
Particle diameter is less than or equal to 100nm, and thickness is 0.4nm, is stirred, and stands 30 min, using pressing speed as 0.05 MPa/min pairs
Liquid adds the MPa of static pressure 10, in the duct that graphene slurry is pressed into porous barium sulfate microballoon, keeps static condition 2.5 hours,
Make graphene is stable to be attached to channel surfaces；
（3）Graphene composite porous microspheres are passed through conventional filtration by removal pressure, add the Silante terminated polyurethane of 8 parts by weight
Performed polymer, polymerize through high-pressure fog and connects, and assembling obtains graphene/porous barium sulfate microballoon composite；
（4）The graphene/porous barium sulfate microballoon composite is scattered in the vector resin polyurethane that parts by weight are 25 parts
In material, 5 parts by weight o-phthalic acid dibutyl esters are added, stirs, automobile is obtained by mechanical presses equipment extruder grain
Engineering plastics special graphite alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment is obtained prepares vapour with 5% mass ratio and 95%ABS blendings
Car bumper, with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch（Directly disperse graphene in vector resin granulation
Arrive）Enhancing performance is compared, and the present embodiment is shown often to be flowed to automobile with the significant enhancement of engineering plastics and good processing
Property.Specific test can be as shown in table 1.
Embodiment 3
（1）It it is 12 parts by parts by weight, particle diameter is the silicon dioxide microsphere of 200nm, sphericity more than 0.9 and 1 weight in 5 μm, aperture
Part phthalic acid ester blending concussion is uniform, and it is 35Hz that frequency is shaken in setting, then to surface modified silicon dioxide porous microsphere
Conventional centrifugal screening is carried out, the rotating speed of centrifugation is 250 rpm, removes the broken microballoon of concussion, obtains intact surface and is modified two
Silicon oxide microsphere；
（2）Surface modified silicon dioxide microballoon is added in pressure vessel, the graphene slurry of 70 parts of parts by weight is added, its is molten
Agent is water, and the graphene slurry of mass concentration 18%, wherein solute graphene are that graphene nanobelt and graphene nanometer sheet are mixed
Powder, the particle diameter of powder is less than or equal to 100nm, and thickness is 1.0nm, is stirred, and 25 min is stood, using pressing speed as 0.05
MPa/min adds the MPa of static pressure 10 to liquid, in the duct that graphene slurry is pressed into porous silica microballoon, keeps standing shape
State 2 hours, makes graphene is stable to be attached to channel surfaces；
（3）Graphene composite porous microspheres are passed through conventional filtration by removal pressure, add the Silante terminated polyurethane of 9 parts by weight
Performed polymer, polymerize through high-pressure fog and connects, and assembling obtains graphene/silicon dioxide porous microsphere composite；
（4）The graphene/silicon dioxide porous microsphere composite is scattered in the polypropylene material that parts by weight are 30 parts,
5 parts by weight diisooctyl phthalates are added, are stirred, obtaining automobile engineering by mechanical presses equipment extruder grain moulds
Expect special graphite alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment is obtained prepares vapour with 5% mass ratio and 95%ABS blendings
Car bumper, with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch（Directly disperse graphene in vector resin granulation
Arrive）Enhancing performance is compared, and the present embodiment is shown often to be flowed to automobile with the significant enhancement of engineering plastics and good processing
Property.Specific test can be as shown in table 1.
Embodiment 4
（1）It it is 15 parts by parts by weight, particle diameter is double stearic for 130nm floating bead microballoon and 0.5 parts by weight ethylene group in 8 μm, aperture
Acid amides blending concussion is uniform, and it is 15Hz to set concussion frequency, then carries out conventional centrifugal screening to surface modified porous microballoon, from
The rotating speed of the heart is 200 rpm, removes the broken microballoon of concussion, obtains intact surface modification floating bead of 90% sphericity more than 0.9 micro-
Ball；
（2）Surface modification floating bead microballoon is added in pressure vessel, 65 parts of graphene slurry is added, solvent is ethanol, solute
Mass concentration be 15% graphene slurry, wherein solute graphene be graphene oxide, redox graphene mixed-powder,
The particle diameter of powder is 50nm, and thickness is 0.8nm, is stirred, and stands 18min, is 0.08 MPa/min to liquid using pressing speed
Plus the MPa of static pressure 20, by the duct of graphene slurry press-in floating bead porous microsphere, keep static condition 2.5 hours, make stone
Black alkene is stable to be attached to channel surfaces；
（3）Removal pressure, is combined floating bead porous microsphere by graphene and passes through conventional filtration, 10 parts by weight of addition are Silante terminated to gather
Urethane performed polymer, polymerize through high-pressure fog and connects, and assembling obtains graphene/floating bead porous microsphere composite；
（4）The graphene/floating bead porous microsphere composite is scattered in the vector resin makrolon that parts by weight are 25 parts
In material and polyurethane material mixture, 4 parts by weight diisooctyl phthalates are added, stirs, passes through conical screw
Equipment extruder grain obtains automobile engineering plastics special graphite alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment is obtained prepares vapour with 5% mass ratio and 95%ABS blendings
Car bumper, with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch（Directly disperse graphene in vector resin granulation
Arrive）Enhancing performance is compared, and the present embodiment is shown often to be flowed to automobile with the significant enhancement of engineering plastics and good processing
Property.Specific test can be as shown in table 1.
Embodiment 5
（1）It it is 10 parts by parts by weight, particle diameter is in the calcium carbonate microspheres and three that 5-12 μm, aperture are that 100-250nm sphericitys are more than 0.9
Al 2 O microballoon is mixed and 0.3 parts by weight lauryl sodium sulfate, the blending of polypropylene wax mixture shake uniform, sets shake
Frequency is swung for 25Hz, conventional centrifugal screening is then carried out to surface modified porous microballoon, the rotating speed of centrifugation is 100-300 rpm,
The broken microballoon of concussion is removed, intact surface is obtained and is modified mixing microballoon；
（2）Surface is modified into mixing microballoon to be added in pressure vessel, graphene slurry is added, solvent is water, and solute concentration is
20% graphene slurry, wherein solute graphene are fluorinated graphene powder, and the particle diameter of powder is 80nm, and thickness is 1.2nm,
Stir, stand 13 min, add the MPa of static pressure 10 to liquid by 0.15 MPa/min of pressing speed, by graphene slurry pressure
In the duct for entering to mix porous microsphere, static condition is kept 2-3 hours, make graphene is stable to be attached to channel surfaces；
（3）Graphene composite porous microspheres are passed through conventional filtration by removal pressure, add the Silante terminated polyurethane of 5 parts by weight
Performed polymer, polymerize through high-pressure fog and connects, and assembling obtains graphene/mixing porous microsphere composite；
（4）Graphene mixing/porous microsphere the composite is scattered in the nylon material that parts by weight are 20 parts, adds 3
Parts by weight o-phthalic acid dibutyl ester, stirs, and it is special to obtain automobile engineering plastics by mechanical presses equipment extruder grain
Graphene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment is obtained prepares vapour with 5% mass ratio and 95%ABS blendings
Car bumper, with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch（Directly disperse graphene in vector resin granulation
Arrive）Enhancing performance is compared, and the present embodiment is shown often to be flowed to automobile with the significant enhancement of engineering plastics and good processing
Property.Specific test can be as shown in table 1.
Table 1：
Claims (7)
1. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch, it is characterized in that being entered by the following raw material according to parts by weight
It is prepared by row：
50-70 parts of graphene slurry；
20-30 parts of vector resin；
10-15 parts of porous microsphere；
5-10 parts of Silante terminated base polyurethane prepolymer for use as；
3-5 parts of modifier；
0.3-1 parts of surfactant；
Specific preparation method is as follows：
（1）By porous microsphere and the uniform progress surface modification of surfactant blending concussion, then to surface modified porous microballoon
Screened, obtain surface modified porous microballoon；
（2）The surface modified porous microballoon is added in pressure vessel, graphene slurry is added, stirs, 10- is stood
30 min, progressively pressurize to pressure vessel, control pressing speed, to static pressure 6-20 MPa, graphene slurry are pressed into porous
In the duct of microballoon, static condition is kept 2-3 hours, make graphene is stable to be attached to channel surfaces；
（3）Graphene composite porous microspheres are passed through conventional filtration by removal pressure, add Silante terminated base polyurethane prepolymer for use as,
It polymerize through high-pressure fog and connects, assembling obtains graphene/porous microsphere composite；
（4）The graphene/porous microsphere composite is scattered in vector resin, modifier is added, stirs,
Automobile engineering plastics special graphite alkene masterbatch is obtained by extruder grain；
Wherein, the mass concentration of the graphene slurry is 10-20%；
The porous microsphere is that particle diameter is 100-250nm, sphericity ＞ 0.85 calcium carbonate microspheres, barium sulfate in 5-12 μm, aperture
At least one of microballoon, floating bead microballoon, hydroxyapatite micro-sphere, alundum (Al2O3) microballoon and silicon dioxide microsphere；
The surfactant is polyamide wax, polypropylene wax, EVA waxes, calcium stearate and magnesium stearate, ethylene group stearic bicine diester
Amine, oleamide, erucyl amide, phthalic acid ester, citrate, lauryl sodium sulfate, dodecyl sodium sulfate and poly-
One or more in vinylpyrrolidone；
The vector resin is at least one of nylon material, polyurethane material, makrolon material, polypropylene material；
The modifier is epoxidized soybean oil, o-phthalic acid dibutyl ester, dioctyl sebacate, the isodecyl of phthalic acid two
One or more of mixtures of ester.
2. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that：Institute
State porous microsphere sphericity ＞ 0.90.
3. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that：Institute
Graphene slurry is stated for single-layer graphene, multi-layer graphene, graphene oxide, redox graphene, fluorinated graphene, graphite
One or more in alkene quantum dot, graphene nanobelt and graphene nanometer sheet and the one or more in water, methanol, ethanol
The graphene slurry of composition.
4. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that：Institute
Stating concussion uses frequency for 10-35Hz magnetic oscillation, filters out sphericity ＞ 0.85 microballoon.
5. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that：Institute
Pressing speed is stated for 0.05-0.15 MPa/min.
6. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that：Institute
The evaporating temperature for stating graphene and porous microsphere mixed solution is 80-160 DEG C.
7. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that：Institute
State extruder grain and use double screw extruder.
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