CN105754310A - Graphene nanoplatelet master batch for enhancing bioplastics and preparation method - Google Patents
Graphene nanoplatelet master batch for enhancing bioplastics and preparation method Download PDFInfo
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- CN105754310A CN105754310A CN201610189912.7A CN201610189912A CN105754310A CN 105754310 A CN105754310 A CN 105754310A CN 201610189912 A CN201610189912 A CN 201610189912A CN 105754310 A CN105754310 A CN 105754310A
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- graphite
- graphene microchip
- polylactic acid
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- graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000704 biodegradable plastic Polymers 0.000 title abstract description 7
- 230000002708 enhancing effect Effects 0.000 title abstract description 3
- 239000002064 nanoplatelet Substances 0.000 title abstract 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 49
- 239000010439 graphite Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 38
- 239000004310 lactic acid Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 30
- 239000004626 polylactic acid Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229920003023 plastic Polymers 0.000 claims description 20
- 239000004033 plastic Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000005728 strengthening Methods 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004067 bulking agent Substances 0.000 claims description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- -1 oxide Chemical compound 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a graphene nanoplatelet master batch for enhancing bioplastics and a preparation method.A lactic acid monomer is conveyed between graphitic layers through solvents to obtain modified graphite, a polycondensation initiator is added, the lactic acid monomer is subjected to a polymerization reaction to obtain polylactic acid macromolecules between the graphitic layers in situ, the distance between the graphitic layers is increased, the acting force between the graphitic layers is lowered, and alternate stacking composite materials of the obtained graphene nanoplatelet/polylactic acid macromolecules are sheared, stripped, extruded and pelletized to obtain the graphene nanoplatelet/polylactic acid composite master batch.Cheap graphite is adopted as a raw material, the production cost can be effectively lowered, the obtained master batch is of a graphene nanoplatelet and polylactic acid alternate stacking wrapping structure, the master batch has the flexibility of graphene and the excellent mechanical performance, and then the defects that bioplastics is low in strength, poor in high temperature resistance and poor in hot workability can be overcome.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, particularly to a kind of graphene microchip masterbatch for strengthening biological plastics and preparation method.
Background technology
Biodegradable plastic be a kind of can promptly by the polymer substance of enzyme or microbial decomposition.Biodegradable plastic, since the eighties is come out, has become the hot issue of new material research always.The leading biodegradable plastic of current China utilizes starch to develop, be desirable Green Polymer Material alternative be raw material with oil plastics, cost is only the 1/5 of oil plastic raw materials.Along with the development of biological plastics technology, in biodegradable plastic, the consumption of starch is also improving constantly, and degradation rate is more and more higher.But, owing to pure polylactic resin material is crisp, processing heat stability is poor, limits its application as engineering plastics.How polylactic resin is strengthened, become the new problem of the industry.
The Two-dimensional Carbon nano material that Graphene is made up of one layer of carbon atom, is be currently known the thinnest two-dimensional material, and its thickness is only 0.335nm, and it is made up of hexagonal lattice, it is possible to regard one layer of graphite flake layer being stripped as.Graphene has the structural rigidity of excellence, makes Graphene have very vast potential for future development.And use Graphene doping macromolecular material to increasingly become study hotspot in functional high polymer material field.
China Patent Publication No. 103467943A provides a kind of glass fiber reinforced polylactic acid biological plastics, is made up of by weight following component: polylactic resin 50-70 part, glass fibre 30-50 part, coupling agent 0.6-1.0 part.The glass fiber reinforced polylactic acid biological plastics of the present invention, improves the mechanical property of polylactic resin.But the shortcoming of this method is in that fiberglass surfacing is smooth, it is necessary to formation potentiation could be bonded with polylactic resin by modified, and glass fibre compliance is poor, it does not have improve the processing characteristics of polylactic resin.
China Patent Publication No. 102030830A discloses nanocrystalline enhancing Biocomposite material of bamboo fibre and preparation method thereof.Starch or protein matrices material are added in glycerin/water, stirs under 30-80 DEG C of condition, add above-mentioned bamboo fibre nanocrystal suspension, after continuing stirring 0.5-3 hour, put in mould flow casting molding under 30-80 DEG C of condition.Nanocrystalline addition substantially increases the mechanical strength of biomaterial.This method utilizes Renewable resource to prepare degradation material, with low cost, and synthesis technique is simple, building-up process green non-pollution, the Product Green environmental protection of gained, and has good biocompatibility.But, the method bamboo fibre complicated process of preparation, manufacturing cycle is long, uses apparatus expensive, and the nanocrystalline also difficulty of dispersion in biomaterial of bamboo fibre accomplishes to be uniformly distributed, it is possible to cause that yield rate is low.
China Patent Publication No. 101484628 discloses a kind of method of strength and stiffness improving fiber.The method graphene film is adhered among carbon filament bundle or yarn or on to form modified fibre, wherein nanoreinforcement material adheres to or is trapped in carbon filament bundle.Modified resin fibre improves notable relative to the fiber stiffness of unmodified resin and strength character, but Graphene is relatively costly, is unfavorable for that large-scale production is promoted.
In sum, with low cost but without a kind of raw materials for production in prior art, and biological plastics low-intensity can be effectively improved, the technological means of heat-resisting quantity is poor, hot-workability is poor defect.
Summary of the invention
In order to solve deficiency and the defect of said method, the present invention develops a kind of graphene microchip masterbatch for strengthening biological plastics and preparation method.Lactic acid monomer is transported to graphite between layers by solvent by the present invention, stand a Preset Time, obtain modified graphite, add polycondensation reaction initiator, lactic acid monomer is obtained polylactic acid macromolecule by polyreaction in graphite layers original position, increase graphite layers distance, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid, then by applying shear action in the high molecular alternative stacked composite of graphene microchip/polylactic acid, natural cooling obtains primary Graphene polylactic acid composite master batch, then sheared by screw extruder and peel off, extruding pelletization obtains Graphene polylactic acid composite master batch.
On the one hand, the present invention provides a kind of graphene microchip masterbatch for strengthening biological plastics, and described masterbatch is prepared from by the raw material including following parts by weight:
Graphite 32-46 part,
Lactic acid monomer 50-66 part,
Plasticizer 1-2 part,
Bulking agent 1-2 part,
Wherein, described graphite is compact crystal shape graphite, one or more in crystalline flake graphite, expanded graphite or expansible graphite, described bulking agent is at least one in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and described plasticizer is aklylene glycol.
Optionally, the structure of described masterbatch is graphene microchip and polylactic acid alternative stacked package structure.
On the other hand, the present invention provides a kind of method peeling off preparing graphite alkene, said method comprising the steps of:
The preparation method of a kind of graphene microchip masterbatch for strengthening biological plastics, said method comprising the steps of:
A. 50-66 part lactic acid monomer and proper amount of surfactant are dissolved in solvent, then 32-46 part graphite is immersed in described solvent, by described solvent, described lactic acid monomer is transported to graphite between layers, after standing a Preset Time, it is thus achieved that modified graphite；
B. 0-1 weight portion polycondensation reaction initiator, 1-2 parts by weight of plasticizer and 1-2 weight portion solubilizing agent are added in solvent, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid；
C. described graphene microchip/polylactic acid polymer composite is taken out from described solvent drying and carries out slicing treatment, graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, extrusion temperature is set and is 100-120 DEG C, shear stripping, extruding pelletization graphene microchip/polylactic acid composite master batch.
Optionally, described surfactant is one or more in vinyltrimethoxy silane, vinyl triethoxyl silicon, sodium lauryl sulphate, dodecyl sodium sulfate and polyvinylpyrrolidone, described solvent is one or more in methanol, ethanol, acetone, described bulking agent is at least one in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and described plasticizer is aklylene glycol.
Optionally, the percentage by weight of described surfactant, described lactic acid monomer and described solvent is 0.05-0.2:34.95-44.8:55-65.
Optionally, in stepb, add polycondensation reaction initiator when described initiation lactic acid monomer generation polycondensation reaction, described polycondensation reaction initiator is the soap of at least one metal in stannum, lead, zinc, titanium, germanium, manganese, magnesium and rare earth element, carbonate, sulfate, phosphate, oxide, hydroxide, alkoxide.
Optionally, the temperature controlling described polycondensation reaction is 100-220 DEG C.
Optionally, in step c, described graphene microchip/polylactic acid polymer composite is taken out from described solvent after drying carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 5-10mm.
Said one in the embodiment of the present application or multiple technical scheme, at least have one or more technique effects following:
1, the present invention adopts lactic acid monomer to serve not only as the remover of graphite material as raw materials for production, and graphene microchip alternative stacked parcel high molecular with polylactic acid, the graphene microchip in masterbatch pellet of preparation can be uniformly distributed at polylactic acid macromolecule, and then the compliance of Graphene and excellent mechanical performance can be utilized, improve the intensity of biomaterial, high temperature resistant and processing characteristics.
2, the present invention adopts lactic acid monomer generation polycondensation reaction at graphite layers fabricated in situ polylactic acid and to obtain graphene microchip, employs conventional biological plastics and graphite as raw material, reduces masterbatch production cost.
3, present invention process is simple, and manufacturing cycle is short, and the equipment cost of use is cheap, is suitable for large-scale production.
Detailed description of the invention
By detailed description of the invention, the present invention is described in further detail, but this should not being interpreted as, the scope of the present invention is only limitted to Examples below.When without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or change, should be included in the scope of the present invention.
Embodiment one
The present embodiment comprises the steps:
The lactic acid monomer of 66 weight portions and surfactant vinyltrimethoxy silane are dissolved in methanol solvate, again the expanded graphite of 32 weight portions is immersed in methanol, wherein, the percentage by weight of vinyl trimethoxy silicon and lactic acid monomer and methanol is 0.05:34.95:65, after standing 12 hours, by methanol, lactic acid monomer is transported to graphite between layers, obtain modified graphite, by 0.5 weight portion polycondensation reaction initiator stearic acid stannum, the aklylene glycol of 1 weight portion and the ethylene-vinyl acetate copolymer of 1 weight portion add in solvent, the temperature controlling polycondensation reaction is 100 DEG C, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid.Graphene microchip/polylactic acid polymer composite is taken out drying from methanol and carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 5-6mm.Graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, and arranging extrusion temperature is 100 DEG C, extruding pelletization, and natural cooling obtains primary Graphene polylactic acid composite master batch.
Embodiment two
The present embodiment comprises the steps:
The lactic acid monomer of 66 weight portions and surfactant vinyl triethoxyl silicon are dissolved in acetone solvent, again by the expanded graphite submergence of 32 weight portions in acetone, wherein, the percentage by weight of vinyl triethoxyl silicon and lactic acid monomer and acetone is 0.05:34.95:65, after standing 12 hours, by acetone, lactic acid monomer is transported to graphite between layers, obtain modified graphite, by 0.5 weight portion polycondensation reaction initiator stearic acid stannum, the aklylene glycol of 1 weight portion and the ethylene-acrylic acid copolymer of 1 weight portion add in solvent, the temperature controlling polycondensation reaction is 100 DEG C, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid.Graphene microchip/polylactic acid polymer composite is taken out drying from acetone and carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 5-6mm.Graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, and arranging extrusion temperature is 100 DEG C, extruding pelletization, and natural cooling obtains primary Graphene polylactic acid composite master batch.
Embodiment three
The present embodiment comprises the steps:
The lactic acid monomer of 66 weight portions and surfactant vinyl triethoxyl silicon are dissolved in acetone solvent, again by the expanded graphite submergence of 32 weight portions in acetone, wherein, the percentage by weight of vinyl triethoxyl silicon and lactic acid monomer and acetone is 0.05:34.95:65, after standing 12 hours, by acetone, lactic acid monomer is transported to graphite between layers, obtain modified graphite, by 0.5 weight portion polycondensation reaction initiator stearic acid stannum, the aklylene glycol of 1 weight portion and the ethylene-vinyl acetate copolymer of 1 weight portion add in solvent, the temperature controlling polycondensation reaction is 220 DEG C, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid.Graphene microchip/polylactic acid polymer composite is taken out drying from acetone and carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 9-10mm.Graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, and arranging extrusion temperature is 100 DEG C, extruding pelletization, and natural cooling obtains primary Graphene polylactic acid composite master batch.
Embodiment four
The present embodiment comprises the steps:
The lactic acid monomer of 50 weight portions and Surfactant SDS are dissolved in acetone solvent, again by the crystalline flake graphite submergence of 46 weight portions in acetone, wherein, the percentage by weight of vinyl triethoxyl silicon and lactic acid monomer and acetone is 0.05:34.95:65, after standing 12 hours, by acetone, lactic acid monomer is transported to graphite between layers, obtain modified graphite, by 0.5 weight portion polycondensation reaction initiator stannous octoate, the aklylene glycol of 2 weight portions and the ethylene-acrylic acid copolymer of 2 weight portions add in solvent, the temperature controlling polycondensation reaction is 220 DEG C, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid.Graphene microchip/polylactic acid polymer composite is taken out drying from acetone and carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 9-10mm.Graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, and arranging extrusion temperature is 120 DEG C, extruding pelletization, and natural cooling obtains primary Graphene polylactic acid composite master batch.
Embodiment five
The present embodiment comprises the steps:
The lactic acid monomer of 50 weight portions and Surfactant SDS are dissolved in acetone solvent, again by the crystalline flake graphite submergence of 46 weight portions in acetone, wherein, the percentage by weight of vinyl triethoxyl silicon and lactic acid monomer and acetone is 0.1:40:59.9, after standing 12 hours, by acetone, lactic acid monomer is transported to graphite between layers, obtain modified graphite, by 0.5 weight portion polycondensation reaction initiator stannous chloride, the aklylene glycol of 1 weight portion and the ethylene-vinyl acetate copolymer of 2 weight portions add in solvent, the temperature controlling polycondensation reaction is 220 DEG C, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid.Graphene microchip/polylactic acid polymer composite is taken out drying from acetone and carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 9-10mm.Graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, and arranging extrusion temperature is 120 DEG C, shears and peels off extruding pelletization, and natural cooling obtains primary Graphene polylactic acid composite master batch.
Although preferred embodiments of the present invention have been described, but those skilled in the art are once know basic creative concept, then these embodiments can be made other change and amendment.So, claims are intended to be construed to include preferred embodiment and fall into all changes and the amendment of the scope of the invention.
Obviously, the present invention can be carried out various change and modification without deviating from the spirit and scope of the present invention by those skilled in the art.So, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (8)
1., for strengthening a graphene microchip masterbatch for biological plastics, described masterbatch is prepared from by the raw material including following parts by weight:
Graphite 32-46 part,
Lactic acid monomer 50-66 part,
Plasticizer 1-2 part,
Bulking agent 1-2 part,
Wherein, described graphite is compact crystal shape graphite, one or more in crystalline flake graphite, expanded graphite or expansible graphite, described bulking agent is at least one in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and described plasticizer is aklylene glycol.
2. the graphene microchip masterbatch being used for strengthening biological plastics, it is characterised in that the structure of described masterbatch is graphene microchip and polylactic acid alternative stacked package structure.
3. the preparation method for strengthening the graphene microchip masterbatch of biological plastics, it is characterised in that said method comprising the steps of:
A. 50-66 part lactic acid monomer and proper amount of surfactant are dissolved in solvent, then 32-46 part graphite is immersed in described solvent, by described solvent, described lactic acid monomer is transported to graphite between layers, after standing a Preset Time, it is thus achieved that modified graphite；
B. 0-1 weight portion polycondensation reaction initiator, 1-2 parts by weight of plasticizer and 1-2 weight portion solubilizing agent are added in solvent, cause lactic acid monomer generation polycondensation reaction, increase graphite gap between layers, reduce graphite layers active force, obtain the high molecular alternative stacked composite of graphene microchip/polylactic acid；
C. described graphene microchip/polylactic acid polymer composite is taken out from described solvent drying and carries out slicing treatment, graphene microchip/polylactic acid polymer composite the microplate obtained is added banburying formula three-screw extruder, extrusion temperature is set and is 100-120 DEG C, shear stripping, extruding pelletization graphene microchip/polylactic acid composite master batch.
4. the preparation method of a kind of graphene microchip masterbatch for strengthening biological plastics according to claim 3, it is characterized in that, described surfactant is one or more in vinyltrimethoxy silane, vinyl triethoxyl silicon, sodium lauryl sulphate, dodecyl sodium sulfate and polyvinylpyrrolidone, described solvent is one or more in methanol, ethanol, acetone, described bulking agent is at least one in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and described plasticizer is aklylene glycol.
5. the preparation method of a kind of graphene microchip masterbatch for strengthening biological plastics according to claim 3, it is characterised in that the percentage by weight of described surfactant, described lactic acid monomer and described solvent is 0.05-0.2:34.95-44.8:55-65.
6. the preparation method of a kind of graphene microchip masterbatch for strengthening biological plastics according to claim 3, it is characterized in that, in stepb, add polycondensation reaction initiator when described initiation lactic acid monomer generation polycondensation reaction, described polycondensation reaction initiator is the soap of at least one metal in stannum, lead, zinc, titanium, germanium, manganese, magnesium and rare earth element, carbonate, sulfate, phosphate, oxide, hydroxide, alkoxide.
7. the preparation method of a kind of graphene microchip masterbatch for strengthening biological plastics according to claim 3, it is characterised in that the temperature controlling described polycondensation reaction is 100-220 DEG C.
8. the preparation method of a kind of graphene microchip masterbatch for strengthening biological plastics according to claim 3, it is characterized in that, in step c, described graphene microchip/polylactic acid polymer composite is taken out from described solvent after drying carries out slicing treatment, it is thus achieved that graphene microchip/polylactic acid polymer composite microplate lamellar spacing is 5-10mm.
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