CN107022183B - 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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- CN107022183B CN107022183B CN201710353718.2A CN201710353718A CN107022183B CN 107022183 B CN107022183 B CN 107022183B CN 201710353718 A CN201710353718 A CN 201710353718A CN 107022183 B CN107022183 B CN 107022183B
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 52
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 47
- -1 graphite alkene Chemical class 0.000 title claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 34
- 239000010439 graphite Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 133
- 239000004005 microsphere Substances 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 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 10
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims abstract description 10
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000003068 static effect Effects 0.000 claims description 14
- 230000009514 concussion Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 239000011324 bead Substances 0.000 claims description 9
- 238000007667 floating Methods 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000001125 extrusion Methods 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 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
- 239000004425 Makrolon Substances 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
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 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
- 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
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000019441 ethanol Nutrition 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
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000007998 bicine buffer Substances 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 239000002096 quantum dot Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 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
- 229920000642 polymer Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003981 vehicle Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 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
- 238000011160 research Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006698 induction Effects 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 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
- 238000006467 substitution reaction 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
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
-
- 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
-
- 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)
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- 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 compound with porous microsphere in advance with slurry form, porous microsphere is set to carry graphene, Silante terminated base polyurethane prepolymer for use as is added, it polymerize through high-pressure fog and connects, is then dispersed in granulation in vector resin and obtains graphene masterbatch.The present invention offer above method overcomes dispersion of the graphene in automobile engineering plastics-production processing use process in the prior art and fails the technological deficiency effectively improved, realize well dispersed technical effect in automobile engineering plastics, and then have the function of high-strength reduction in automobile engineering plastic applications, it is the critical material of automotive light weight technology.In particular, the graphene masterbatch because high sphericity microballoon there are due to there is high fluidity, be exclusively used in automobile engineering plastics, ordinary graphite alkene masterbatch effectively overcome to be difficult to flow the defect of dispersion.The scheme preparation process 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 fields, and in particular to a kind of preparation of automobile engineering plastics special graphite alkene masterbatch
Method.
Background technique
With the rise of automotive light weight technology, automobile plastic components using more and more.Automobile is moulded by developed country
Doses accounts for integral material with plastics as an important symbol for measuring Automobile Design and manufacture level height, German automobiles
15%.China's development of automobile industry is rapid in recent years, and automobile annual output is more than 4,000,000 at present, referring to external trend, automobile
Industry year will be at 500,000 tons or more with modified plastics, and wherein engineering plastics account for a big chunk ratio, and it is various to be applied to automobile
Components.However facing to automobile lighting, high strengthening development trend, the modification of existing engineering plastics has been difficult to meet automobile
The demand of development.
It was the Andre Geim as Univ Manchester UK earliest made from 2004 that graphite is dilute.It is to be currently known most
Thin two-dimensional material, thickness are only 0.335nm, it is made of the lattice of six sides.Dilute graphite is considered as fowler coal, carbon nanometer
The basic structural unit of pipe, graphite is paid high attention to because its mechanics, quantum and electrical properties are special by physics and material educational circles.
Graphene is the nano material that known world is most thin, most hard, and the dilute stretch modulus of graphite and ultimate strength are received with single armed carbon
It is suitable to carry out pipe, light weight, thermal conductivity is good and large specific surface area.Graphene becomes from now on as a kind of high-performance reinforcing material
The first choice of automobile specified plastics.
Have it with form of single sheet from stable since graphene has stronger model ylid bloom action power each other, stone
Black alkene is once reunited stacking, and thermal conductivity, which will appear, sharply to be declined, and once occur layer heap it is folded if graphene it is difficult between layers
To open, need to remove again.More research at present is that the dispersibility of graphene is improved by dispersing agent, but due to graphite
Alkene is different from common inorganic particle, and conventional dispersing agent and dispersion means are difficult to reach dispersion effect.However automobile engineering is moulded
Expect usual poor fluidity, graphene dispersion is wherein more 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 using surface modifier and by electrostatic self-assembled technology,
Graphene/carbon black hybrid material is prepared, the reunion of graphene in last handling process is effectively prevented, obtains the stone of good dispersion
Black alkene masterbatch.But the problem of facing the dissipation of charge in preparation and storing process, it is more demanding to technique continuity.
Chinese Patent Application No. 201510916570.X discloses a kind of raising graphene to be dispersed in a polymer matrix
Method, using lewis acid catalyst by the graft reaction of induction during melt-processed, so that in the masterbatch system of preparation
Graphene surface has been grafted long-chain molecule, and the graphene and polymer of long-chain grafting are diluted compound tense by melt-processed,
It can significantly improve the dispersion of graphene in the base.Although the generation that this method can inhibit graphene to reunite, this
It needs to accurately control reaction condition, and uses special organic catalyst, working condition is more harsh, is unfavorable for extensive work
Industry metaplasia produces.
It follows that improve dispersibility of the graphene in production and processing use process, it is necessary to propose a kind of can have
Effect solves the problems, such as that graphene is easy to reunite, improves uniformly dispersed preparation method 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 more difficult.It realizes graphene and enhances in automobile engineering plastics, light-weighted extensive use, primarily solve graphene
High flowing dispersibility.
Summary of the invention
Fail effectively to mention for dispersion of the graphene in the prior art in automobile engineering plastics-production processing use process
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, so that 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 overcomes
It is scarce to fail the technology effectively improved for dispersion of the graphene in automobile engineering plastics-production processing use process in the prior art
It falls into, realizes well dispersed technical effect in automobile engineering plastics, and then with high-strength in automobile engineering plastic applications
The effect for spending minimizing, is the critical material of automotive light weight technology.In particular, the graphene masterbatch because high sphericity microballoon there are due to
With high fluidity, automobile engineering plastics are exclusively used in, ordinary graphite alkene masterbatch is effectively overcome to be difficult to flow the defect of dispersion.Invention
Disclosed scheme preparation process is simple, it is easy to accomplish scale industrial production.
To solve the above problems, the invention adopts the following technical scheme:
A kind of preparation method of automobile engineering plastics special graphite alkene masterbatch, it is characterized in that by the following raw material according to parts by weight
It is prepared:
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；
It is specific the preparation method is as follows:
(1) concussion is blended in porous microsphere and surfactant to be uniformly modified on progress surface, then to surface modified porous
Microballoon is screened, and surface modified porous microballoon is obtained；
(2) the surface modified porous microballoon is added in pressure vessel, graphene slurry is added, stirs evenly, it is quiet
10-30 min is set, is gradually pressurizeed to pressure vessel, pressing speed is controlled, until static pressure 6-20 MPa, graphene slurry is pressed into
It in the duct of porous microsphere, is kept for static condition 2-3 hours, graphene stabilization is made to be attached to channel surfaces；
(3) graphene composite porous microspheres are passed through conventional filtration, Silante terminated polyurethane prepolymer are added by removal pressure
Body polymerize through high-pressure fog and connects, and assembling obtains graphene/porous microsphere composite material；
(4) it disperses the graphene/porous microsphere composite material in vector resin, modifier, stirring is added
Uniformly, automobile engineering plastics special graphite alkene masterbatch is obtained by extrusion granulation；
Wherein, the mass concentration of the graphene slurry is 10-20%；
The porous microsphere is partial size in 5-12 μm, aperture 100-250nm, the calcium carbonate microspheres of sphericity > 0.85, sulphur
At least one of sour barium microballoon, floating bead microballoon, hydroxyapatite micro-sphere, aluminum oxide microballoon and silicon dioxide microsphere；
The surfactant is that polyamide wax, polypropylene wax, EVA wax, calcium stearate and magnesium stearate, ethylene group are double hard
Acyl amine, oleamide, erucyl amide, phthalic acid ester, citrate, lauryl sodium sulfate, dodecyl sodium sulfate
One or more of with polyvinylpyrrolidone.
The vector resin is nylon material, polyurethane material, makrolon material, at least one in polypropylene material
Kind；
The modifier is epoxidized soybean oil, dioctyl phthalate, dioctyl sebacate, phthalic acid two
One or more of mixtures of isodecyl ester.
Have it with form of single sheet from stable since graphene has stronger model ylid bloom action power each other, stone
Black alkene is once reunited stacking, and thermal conductivity, which will appear, sharply to be declined, and once occur layer heap it is folded if graphene it is difficult between layers
To open, need to remove again.More research at present is that the dispersibility of graphene is improved by dispersing agent, but due to graphite
Alkene is different from common inorganic particle, and conventional dispersing agent and dispersion means are difficult to reach dispersion effect.However automobile engineering is moulded
Expect usual poor fluidity, graphene dispersion is wherein more difficult.In consideration of it, to propose that one kind can effectively solve graphene easy by the present invention
The problem of reunion, improves uniformly dispersed preparation method of the graphene in masterbatch, by graphene with slurry form in advance with
High sphericity porous microsphere is compound, and porous microsphere is made to carry graphene, by the way that Silante terminated base polyurethane prepolymer for use as is added, through high pressure
Spraying, significant advantage is that Silante terminated base polyurethane prepolymer for use as in porous microsphere surface aggregate, and again under high pressure disperses shape
At the microballoon fixed one by one by thermoplastic polyurethane film, with good dispersibility, further stable stone while dispersion
Black alkene prevents its reunion.The rolling action of high sphericity microballoon and high fluidity are dispersed in graphene high-efficiency in vector resin
Obtain graphene masterbatch, in particular, the graphene masterbatch because high sphericity microballoon there are due to there is high fluidity, be exclusively used in automobile
Engineering plastics effectively overcome ordinary graphite alkene masterbatch to be difficult to flow the defect of dispersion.
Although mobility can be improved by improving the lubricants such as wax, it will be clear that mistake in automobile engineering plastic processing
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 dispersion of graphene, and the masterbatch is made 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 protrudes compared with prior art
The characteristics of and excellent effect be:
1, the preparation method of a kind of automobile engineering plastics special graphite alkene masterbatch provided by the invention, by graphene with slurry
Form is compound with high sphericity porous microsphere in advance, so that porous microsphere is carried graphene, Silante terminated base polyurethane prepolymer for use as is added,
It polymerize through high-pressure fog and connects, it is firmly, so that high efficiency dispersion obtains graphene masterbatch in vector resin that this, which is combined,.
2, by the present invention in that carrying graphene with high sphericity porous microsphere, the dispersion of graphene is not only solved,
And make the masterbatch that there is good processing fluidity in automobile engineering plastics.
3, scheme preparation process 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 suitable for substitution carbon fiber, glass fibre be used for front/rear collision bumper, automobile interior decoration,
Automobile case, radiator etc., have the function of high-strength reduction, are the critical materials of automotive light weight technology.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) by parts by weight be 10 parts, partial size 5 μm, aperture 250nm, sphericity be greater than 0.85 calcium carbonate microspheres and
Concussion is blended uniformly in 0.3 weight parts of polyamide wax, and setting oscillation frequency is 10Hz, then micro- to the modified porous calcium carbonate in surface
Ball carries out conventional centrifugal screening, and the revolving speed of centrifugation is 300 rpm, removes the broken microballoon of concussion, and it is complete greater than 0.85 to obtain sphericity
Good 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 solvent is water, and mass concentration 10%, wherein solute graphene is single-layer graphene and multi-layer graphene mixed-powder, powder
The partial size at end is 100nm, and thickness is less than 1.6nm, stirs evenly, and 10-30 min is stood, with pressing speed for 0.05 MPa/min
20 MPa of liquid plus static pressure is kept in the duct of graphene slurry indentation porous calcium carbonate microballoon for static condition 2 hours,
Graphene stabilization is set to be attached to channel surfaces；
(3) graphene composite porous microspheres are passed through conventional filtration by removal pressure, and 5 parts by weight of addition are Silante terminated to gather
Urethane performed polymer polymerize through high-pressure fog and connects, and assembling obtains graphene/porous calcium carbonate microballoon composite material；
(4) it disperses the graphene/porous calcium carbonate microballoon composite material in the nylon material that parts by weight are 20 parts,
5 parts by weight epoxy soybean oils are added, stir evenly, the dedicated stone of automobile engineering plastics is obtained by double screw extruder extrusion granulation
Black alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment obtains is blended with 5% mass ratio with 95%ABS and prepares vapour
Vehicle bumper (directly disperses graphene in vector resin to be granulated with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch
To) enhancing performance compare, the present embodiment show to automobile often with the significant enhancement of engineering plastics and good processing flowing
Property.Specific test can be as shown in table 1.
Embodiment 2
(1) by parts by weight be 15 parts, partial size 10 μm, aperture be 250nm sphericity greater than 0.85 barium sulfate microballoon and
Concussion is blended uniformly in 0.5 weight parts of polyamide wax, and setting oscillation frequency is 35Hz, then carries out to surface modified porous microballoon normal
Centrifugal screening is advised, the revolving speed of centrifugation is 130 rpm, removes the broken microballoon of concussion, it is micro- to obtain intact surface modified barium sulphate
Ball；
(2) surface modified barium sulphate microballoon is added in pressure vessel, the graphene slurry that parts by weight are 60 is added,
The graphene slurry that solvent is water, Solute mass concentration is 15%, wherein solute graphene is redox graphene powder, powder
The partial size at end is less than or equal to 100nm and stirs evenly with a thickness of 0.4nm, stands 30 min, with pressing speed for 0.05 MPa/
Min adds 10 MPa of static pressure to liquid, graphene slurry is pressed into the duct of porous barium sulfate microballoon, keeps static condition 2.5
Hour, so that graphene stabilization is attached to channel surfaces；
(3) graphene composite porous microspheres are passed through conventional filtration by removal pressure, 8 parts by weight of addition are Silante terminated to gather
Urethane performed polymer polymerize through high-pressure fog and connects, and assembling obtains graphene/porous barium sulfate microballoon composite material；
(4) vector resin that parts by weight are 25 parts is dispersed by the graphene/porous barium sulfate microballoon composite material to gather
In urethane material, 5 parts by weight dioctyl phthalates are added, stirs evenly, is obtained by mechanical presses equipment extrusion granulation
Automobile engineering plastics special graphite alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment obtains is blended with 5% mass ratio with 95%ABS and prepares vapour
Vehicle bumper (directly disperses graphene in vector resin to be granulated with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch
To) enhancing performance compare, the present embodiment show to automobile often with the significant enhancement of engineering plastics and good processing flowing
Property.Specific test can be as shown in table 1.
Embodiment 3
It (1) is 12 parts by parts by weight, partial size is greater than 0.9 silicon dioxide microsphere and 1 in 5 μm, aperture 200nm, sphericity
Concussion is blended uniformly in parts by weight phthalic acid ester, and setting oscillation frequency is 35Hz, then porous to surface modified silicon dioxide
Microballoon carries out conventional centrifugal screening, and the revolving speed of centrifugation is 250 rpm, removes the broken microballoon of concussion, obtains intact surface and change
Property silicon dioxide microsphere；
(2) surface modified silicon dioxide microballoon is added in pressure vessel, 70 parts of parts by weight of graphene slurry is added,
Its solvent is water, and the graphene slurry of mass concentration 18%, wherein solute graphene is graphene nanobelt and graphene nanometer sheet
Mixed-powder, the partial size of powder are less than or equal to 100nm and stir evenly with a thickness of 1.0nm, stand 25 min, be with pressing speed
0.05 MPa/min adds 10 MPa of static pressure to liquid, by the duct of graphene slurry indentation porous silica microballoon, keeps
Static condition 2 hours, graphene stabilization is made to be attached to channel surfaces；
(3) graphene composite porous microspheres are passed through conventional filtration by removal pressure, and 9 parts by weight of addition are Silante terminated to gather
Urethane performed polymer polymerize through high-pressure fog and connects, and assembling obtains graphene/silicon dioxide porous microsphere composite material；
(4) polypropylene material that parts by weight are 30 parts is dispersed by the graphene/silicon dioxide porous microsphere composite material
In material, 5 parts by weight diisooctyl phthalates are added, stirs evenly, automobile is obtained by mechanical presses equipment extrusion granulation
Engineering plastics special graphite alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment obtains is blended with 5% mass ratio with 95%ABS and prepares vapour
Vehicle bumper (directly disperses graphene in vector resin to be granulated with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch
To) enhancing performance compare, the present embodiment show to automobile often with the significant enhancement of engineering plastics and good processing flowing
Property.Specific test can be as shown in table 1.
Embodiment 4
It (1) is 15 parts by parts by weight, partial size is double in 8 μm, the floating bead microballoon that aperture is 130nm and 0.5 parts by weight ethylene group
Concussion is blended uniformly in stearmide, and setting oscillation frequency is 15Hz, then carries out conventional centrifugal sieve to surface modified porous microballoon
Choosing, the revolving speed of centrifugation are 200 rpm, remove the broken microballoon of concussion, and it is modified to obtain intact surface of 90% sphericity greater than 0.9
Floating bead microballoon；
(2) the modified floating bead microballoon in surface being added in pressure vessel, is added 65 parts of graphene slurry, solvent is ethyl alcohol,
The graphene slurry that Solute mass concentration is 15%, wherein solute graphene is graphene oxide, redox graphene mixed powder
End, the partial size of powder are that 50nm stirs evenly with a thickness of 0.8nm, stand 18min, are 0.08 MPa/min pairs with pressing speed
Liquid adds 20 MPa of static pressure, by the duct of graphene slurry indentation floating bead porous microsphere, is kept for static condition 2.5 hours, is made
Graphene stabilization is attached to channel surfaces；
(3) the compound floating bead porous microsphere of graphene is passed through conventional filtration, it is Silante terminated that 10 parts by weight is added by removal pressure
Base polyurethane prepolymer for use as, through high-pressure fog polymerize connect, assembling obtain graphene/floating bead porous microsphere composite material；
(4) the poly- carbon of vector resin that parts by weight are 25 parts is dispersed by the graphene/floating bead porous microsphere composite material
In acid esters material and polyurethane material mixture, 4 parts by weight diisooctyl phthalates are added, stirs evenly, passes through taper
Screw apparatus extrusion granulation obtains automobile engineering plastics special graphite alkene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment obtains is blended with 5% mass ratio with 95%ABS and prepares vapour
Vehicle bumper (directly disperses graphene in vector resin to be granulated with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch
To) enhancing performance compare, the present embodiment show to automobile often with the significant enhancement of engineering plastics and good processing flowing
Property.Specific test can be as shown in table 1.
Embodiment 5
It (1) is 10 parts by parts by weight, partial size is in the calcium carbonate microspheres that 5-12 μm, aperture are that 100-250nm sphericity is greater than 0.9
Concussion is blended uniformly with the mixing of aluminum oxide microballoon and 0.3 parts by weight lauryl sodium sulfate, polypropylene wax mixture, if
Setting oscillation frequency is 25Hz, then carries out conventional centrifugal screening to surface modified porous microballoon, and the revolving speed of centrifugation is 100-300
Rpm removes the broken microballoon of concussion, obtains the modified mixing microballoon in intact surface；
(2) the modified mixing microballoon in surface is added in pressure vessel, graphene slurry is added, solvent is water, and solute is dense
The graphene slurry that degree is 20%, wherein solute graphene is fluorinated graphene powder, and the partial size of powder is 80nm, with a thickness of
1.2nm is stirred evenly, and stands 13 min, is that 0.15 MPa/min adds 10 MPa of static pressure to liquid with pressing speed, by graphene
In the duct of slurry indentation mixing porous microsphere, is kept for static condition 2-3 hours, graphene stabilization is made to be attached to channel surfaces；
(3) graphene composite porous microspheres are passed through conventional filtration by removal pressure, and 5 parts by weight of addition are Silante terminated to gather
Urethane performed polymer polymerize through high-pressure fog and connects, and assembling obtains graphene/mixing porous microsphere composite material；
(4) it disperses the graphene mixing/porous microsphere composite material in the nylon material that parts by weight are 20 parts, adds
Enter 3 parts by weight dioctyl phthalates, stir evenly, it is special to obtain automobile engineering plastics by mechanical presses equipment extrusion granulation
With graphene masterbatch.
The automobile engineering plastics special graphite alkene masterbatch that embodiment obtains is blended with 5% mass ratio with 95%ABS and prepares vapour
Vehicle bumper (directly disperses graphene in vector resin to be granulated with 10% fiberglass reinforced masterbatch, 10% commercially available graphene masterbatch
To) enhancing performance compare, the present embodiment show to automobile often with the significant enhancement of engineering plastics and good processing flowing
Property.Specific test can be as shown in table 1.
Table 1:
Claims (6)
1. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch, it is characterized in that by the following raw material according to parts by weight into
Row preparation:
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；
It is specific the preparation method is as follows:
(1) concussion is blended in porous microsphere and surfactant to be uniformly modified on progress surface, then to surface modified porous microballoon
It is screened, obtains surface modified porous microballoon；
(2) the surface modified porous microballoon is added in pressure vessel, graphene slurry is added, stirs evenly, stand 10-
30min gradually pressurizes to pressure vessel, controls pressing speed, until static pressure 6-20MPa, graphene slurry is pressed into porous micro-
It in the duct of ball, is kept for static condition 2-3 hours, graphene stabilization is made to be attached to channel surfaces；
(3) graphene composite porous microspheres are passed through conventional filtration, Silante terminated base polyurethane prepolymer for use as are added by removal pressure,
It polymerize through high-pressure fog and connects, assembling obtains graphene/porous microsphere composite material；
(4) it disperses the graphene/porous microsphere composite material in vector resin, modifier is added, stirs evenly,
Automobile engineering plastics special graphite alkene masterbatch is obtained by extrusion granulation；
Wherein, the mass concentration of the graphene slurry is 10-20%；
The porous microsphere is partial size in 5-12 μm, aperture 100-250nm, the calcium carbonate microspheres of sphericity > 0.85, barium sulfate
At least one of microballoon, floating bead microballoon, hydroxyapatite micro-sphere, aluminum oxide microballoon and silicon dioxide microsphere；
The surfactant is polyamide wax, polypropylene wax, EVA wax, calcium stearate, magnesium stearate, ethylene group stearic bicine diester
Amine, oleamide, erucyl amide, phthalic acid ester, citrate, lauryl sodium sulfate, dodecyl sodium sulfate, poly- second
One or more of alkene pyrrolidone.
The vector resin is at least one of nylon material, polyurethane material, makrolon material, polypropylene material；
The modifier is epoxidized soybean oil, dioctyl phthalate, dioctyl sebacate, two isodecyl of phthalic acid
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
Stating graphene slurry is single-layer graphene, multi-layer graphene, graphene oxide, redox graphene, fluorinated graphene, graphite
One or more of alkene quantum dot, graphene nanobelt and graphene nanometer sheet and one or more of water, methanol, ethyl alcohol
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
The magnetic oscillation that concussion uses frequency as 10-35Hz is stated, the microballoon of sphericity > 0.85 is filtered out.
5. a kind of preparation method of automobile engineering plastics special graphite alkene masterbatch according to claim 1, it is characterised in that: institute
Stating pressing speed is 0.05-0.15MPa/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
Extrusion granulation is stated using double screw extruder.
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| CN109762305B (en) * | 2019-01-22 | 2021-09-10 | 宁波石墨烯创新中心有限公司 | Graphene master batch and preparation method thereof |
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