CN116199971A - Easily-sprayed conductive micro-foaming polypropylene material and preparation method and application thereof - Google Patents
Easily-sprayed conductive micro-foaming polypropylene material and preparation method and application thereof Download PDFInfo
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- CN116199971A CN116199971A CN202211685824.8A CN202211685824A CN116199971A CN 116199971 A CN116199971 A CN 116199971A CN 202211685824 A CN202211685824 A CN 202211685824A CN 116199971 A CN116199971 A CN 116199971A
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- -1 polypropylene Polymers 0.000 title claims abstract description 77
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 238000005187 foaming Methods 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 69
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 239000007921 spray Substances 0.000 claims abstract description 29
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 229920001897 terpolymer Polymers 0.000 claims abstract description 6
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims abstract description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000004156 Azodicarbonamide Substances 0.000 claims description 11
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 11
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- KZGROEDUAFPSGN-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphate Chemical compound CC(C)(C)C1=CC=C(OP(O)(O)=O)C(C(C)(C)C)=C1 KZGROEDUAFPSGN-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 238000005507 spraying Methods 0.000 abstract description 17
- 239000004020 conductor Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000002109 single walled nanotube Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- ROMCRKSGDFOTBY-UHFFFAOYSA-N CCC[SiH2]C Chemical compound CCC[SiH2]C ROMCRKSGDFOTBY-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses an easy-to-spray conductive micro-foaming polypropylene material and a preparation method and application thereof, and relates to the field of high polymer materials. The conductive micro-foaming polypropylene material easy to spray comprises one or more of polypropylene resin, a toughening agent, a carbon nano tube, a polar copolymer, a foaming agent, a compatilizer, an antioxidant and a polar copolymer, wherein the polar copolymer is polyvinyl chloride, ethylene-acrylic ester-glycidyl methacrylate terpolymer and ethylene-methyl methacrylate copolymer. The foaming agent is utilized to provide self foaming function, the carbon nanotube material is adopted to provide conductivity, and the polar copolymer improves the polarity of the polypropylene material, so that the effect of improving the easiness in spraying is achieved, the light weight, the conductivity and the easiness in spraying of the conductive material are considered, the limitation of the conductive material on the appearance is broken through, the appearance possibility of the material is greatly expanded, the comprehensive performance is superior, and the application field is widened.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an easy-to-spray conductive micro-foaming polypropylene material and a preparation method and application thereof.
Background
Conductive polypropylene is widely applied and has mature application in the fields of packaging, trays and the like, but the current requirements for light weight and diversified appearance are more and more. At present, the light weight method mainly comprises foaming treatment and the appearance diversification method mainly comprises spraying treatment. However, the spraying requires various surface treatments and then printing spraying, so that the field is also lack of foaming spraying conductive polypropylene products.
At present, the high efficiency of curing the thermosetting polymer by utilizing microwaves and the strong absorption of microwave active low molecular substances to the microwaves are utilized, the low molecular substances absorb the microwaves to gasify while the polymer is cured, and the curing and the foaming are simultaneously carried out to form the polymer foam material. However, the method is limited in application, cannot be used in the injection molding field, has single performance, and cannot have the functions of conductivity and easiness in spraying.
Disclosure of Invention
The invention provides an easy-to-spray conductive micro-foaming polypropylene material, and a preparation method and application thereof, so as to provide a foaming polypropylene material which is light in weight, easy to spray and excellent in conductive performance.
In order to solve the technical problems, one of the purposes of the invention is to provide an easy-to-spray conductive micro-foaming polypropylene material which comprises the following components in parts by weight:
polypropylene resin: 54-80 parts;
toughening agent: 12-20 parts;
carbon nanotubes: 0.5-10 parts;
polar copolymer: 3-11 parts;
foaming agent: 1-2 parts;
and (3) a compatilizer: 1-3 parts;
an antioxidant: 0.1 to 0.5 part;
wherein the polar copolymer is one or more of polyvinyl chloride, ethylene-acrylic ester-glycidyl methacrylate terpolymer and ethylene-methyl methacrylate copolymer.
By adopting the scheme, the foaming agent is utilized to provide self foaming function, the carbon nanotube material is utilized to replace conductive carbon black to provide conductive performance, and as the influence of the carbon nanotube on the foaming performance of the system is extremely low, the dispersion of the carbon nanotube in the polypropylene system is further improved by the compatilizer, and meanwhile, the conductive performance of the carbon nanotube is obviously better than that of the conductive carbon black, the addition amount and cost of the filler in the system can be reduced, so that the influence of the carbon nanotube material on foaming is reduced to the minimum, and the effects of light weight and low density can be achieved while the superior conductive performance is met; the polar copolymer can improve the polarity of the polypropylene material, and the change of the polarity can strengthen the adhesion between the ink and the surface, so that the effect of improving the easiness in spraying is achieved, and the carbon nano tube adopted by the application can not have the condition that carbon powder falls due to the increase of the content, so that the influence of the material on the surface spraying effect is avoided; the polypropylene material finally obtained through the synergistic combination of the components and the component contents has the effects of conductivity, light weight and easiness in spraying, and has excellent comprehensive performance, so that the application field is widened.
Preferably, the compatilizer is one or more of maleic anhydride grafted PE, maleic anhydride grafted PP, 2-2-trimethoxysilylpropyl methyl silane and 3-glycidoxypropyl trimethoxy silane.
Preferably, the polypropylene resin has a melt strength of > 30cN when tested at 190 ℃.
Through adopting above-mentioned scheme, the melt strength of polypropylene resin is lower to foaming has the influence, and melt strength is less can influence foaming effect for the product foaming is inhomogeneous, leads to product whole resistance distribution inhomogeneous, and control polypropylene resin's melt strength is greater than 30cN, can guarantee foaming effect, improves lightweight performance and resistance performance.
As a preferable scheme, the melt strength of the polypropylene resin is 31-45cN under the test of 190 ℃, so that poor melt fluidity caused by too high melt strength can be avoided, and the influence on processability is avoided.
As a preferred embodiment, the melt strength of the polypropylene resin is measured using a melt strength tester which uniaxially stretches the polymer melt, the melt is first extruded downwardly from an extrusion die while being pulled by two rolls mounted on a balance beam in opposite directions of movement, the force applied to the melt strand as it is stretched is the uniform acceleration of the rolls until the melt strand breaks, the force applied to the break of the melt strand being defined as "melt strength".
Preferably, the foaming agent is one or more of azodicarbonamide, sodium bicarbonate, citric acid, sodium carbonate, ammonium carbonate, 4' -oxo-bis-benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide and dinitroso pentamethylene tetramine.
As a preferable scheme, the novel high-performance polyurethane foam also comprises 0.3 to 0.7 part by weight of white oil, 0.1 to 0.5 part by weight of 2,2' -methylenebis (4, 6-di-tert-butylphenyl phosphate) basic aluminum and 0.2 to 0.5 part by weight of polysiloxane.
By adopting the scheme, the white oil, polysiloxane and 2,2' -methylenebis (4, 6-di-tert-butylphenyl phosphate) basic aluminum added in the method are beneficial to improving the dispersibility of the carbon nano tube and integrally improving the processability of the product.
Preferably, at least one of the following (1) to (3) is contained:
(1) The polar copolymer is an ethylene-acrylic ester-glycidyl methacrylate terpolymer;
(2) The compatilizer is maleic anhydride grafted PE;
(3) The foaming agent is azodicarbonamide foaming agent or azodicarbonamide foaming master batch.
As a preferable scheme, the azodicarbonamide foaming master batch contains 25-35wt% of PE carrier and 65-75wt% of azodicarbonamide.
By adopting the scheme, the compatibility of the carbon nano tube and the polar copolymer with the polypropylene resin is synchronously improved by adopting the maleic anhydride grafted PE, so that the conductivity, foaming and easy spraying performance of the material are improved. The polar copolymer contains high-activity ethyl and epoxy groups, and the high-polarity groups have higher orientation force and induction force, so that the high-polarity groups are easier to interact with components in the ink to form hydrogen bonds and the like, so that the interaction of the ink is stronger, carbon nanotubes uniformly dispersed in the material can avoid the situation of dropping carbon powder, and are harder to drop, and the adhesive force is stronger. After the polar copolymer, the compatilizer and the foaming agent are combined by the specific three components, the conductivity, the light weight and the easy spraying effect of the product are further improved, and the comprehensive effect is optimal.
Preferably, the grafting rate of the maleic anhydride grafted PE and the maleic anhydride grafted PP is 0.7-1.5%.
Preferably, the toughening agent is one or more of ethylene-octene copolymer, ethylene-propylene-diene terpolymer (EPDM), ethylene Propylene Rubber (EPR), styrene-butadiene thermoplastic elastomer (SBS) and ethylene-vinyl acetate copolymer (EVA).
Preferably, the antioxidant is hindered phenol antioxidant and/or phosphite antioxidant.
Preferably, the carbon nanotubes comprise the following components in percentage by mass (0.8-1.5): 2 and multi-walled carbon nanotubes.
By compounding the single-wall carbon nanotubes and the multi-wall carbon nanotubes, the influence of the carbon nanotubes on the mechanical properties can be reduced while the better conductive properties are met, and the cantilever impact strength of the conductive foaming material is improved.
As a preferable scheme, the antioxidant comprises 1010 and 168 in mass ratio of (1-3): 1.
Preferably, the carbon nanotubes are single-walled carbon nanotubes.
In order to solve the technical problems, the second object of the present invention is to provide a method for preparing a conductive micro-foaming polypropylene material easy to spray, comprising the following steps:
(1) Putting the components into a high-speed mixer, fully stirring, and uniformly mixing to obtain a premix;
(2) And (3) placing the premix into a main feeding port of double-screw extrusion equipment for melting, extruding, granulating and drying, wherein the melting extrusion temperature is 150-220 ℃, the main machine rotating speed is 300-600r/min, and the length-diameter ratio of the double-screw extruder is (10-50): 1, so that the conductive micro-foaming polypropylene material easy to spray is obtained.
In order to solve the technical problems, the invention provides an application of the conductive micro-foaming polypropylene material easy to spray in the fields of dustproof packaging and antistatic transfer boxes.
The anti-static and dustproof packaging box is particularly applied to the electronic packaging industry, and compared with the PP+carbon black injection molding box body which is used at present more and distinguished by repeated labeling, the anti-static and dustproof packaging box is characterized in that the material can be directly marked in a pad printing mode and the like, the weight can be reduced, and meanwhile, the pollution of carbon dropping to a precise electronic element can be reduced due to the replacement of conductive filler.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. the foaming agent is utilized to provide self foaming function, the carbon nanotube material is adopted to replace conductive carbon black to provide conductive performance, and meanwhile, the compatilizer is utilized to improve the dispersion of the carbon nanotube material in a polypropylene system, so that the influence of the carbon nanotube material on foaming is reduced to the minimum, and the effects of light weight and low density can be achieved while the superior conductive performance is met.
2. On the basis of meeting filler dispersion, foaming and electric conduction, the polarity of the polypropylene material is improved by utilizing the polar copolymer, the adhesive force between the printing ink and the surface of a product can be stronger by combining the foaming agent with the change of the polarity, and carbon nano tubes can be used for replacing the electric conduction material to avoid carbon powder falling and influencing the spraying, so that the effect of improving the easy spraying is achieved.
3. According to the method, the components and the component contents are matched in a synergistic manner, so that the obtained polypropylene material greatly improves the sprayability of the material, the weight reduction and the conductivity of the conductive material are considered, the limitation of the conductive material on the appearance is broken through, the appearance possibility of the material is greatly expanded, the comprehensive performance is excellent, and the application field is widened.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The sources and performance parameters of the raw materials in the following examples and comparative examples are shown in Table 1, and the antioxidant, carbon nanotube, white oil, polysiloxane, 2 '-methylenebis (4, 6-di-t-butylphenyl phosphate) basic aluminum are all commercially available, and the same antioxidant, carbon nanotube, white oil, polysiloxane, 2' -methylenebis (4, 6-di-t-butylphenyl phosphate) basic aluminum was used in parallel test.
TABLE 1 sources of raw materials and Performance parameters in examples and comparative examples of the present application
Examples 1 to 9
An easy-to-spray conductive micro-foaming polypropylene material, as shown in Table 2, comprises polypropylene resin, a toughening agent, carbon nano tubes, a polar copolymer, a foaming agent, a compatilizer, an antioxidant, white oil, 2' -methylenebis (4, 6-di-tert-butylphenyl phosphoric acid) basic aluminum and polysiloxane; the toughening agent is an ethylene-octene copolymer; the compatilizer is maleic anhydride grafted PP, maleic anhydride grafted PE or 2-2-trimethoxy silicon-based propyl methyl silane; the polar copolymer is ethylene-acrylic ester-glycidyl methacrylate terpolymer; the foaming agent is azodicarbonamide foaming master batch; the antioxidant comprises 1010 and 168 in mass ratio of 1:1, compounding; the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
The preparation method of the conductive micro-foaming polypropylene material easy to spray comprises the following steps:
(1) Putting the components into a high-speed mixer, fully stirring, and uniformly mixing to obtain a premix;
(2) Placing the premix into a main feeding port of a double-screw extruder for melting, extruding, granulating and drying, wherein the condition of the melting extrusion temperature is 150-220 ℃, and the rotating speed of a host machine is 400 r/min; the length-diameter ratio of the double-screw extruder is 40:1, and the conductive micro-foaming polypropylene material easy to spray is obtained.
TABLE 2 Components and contents in examples 1 to 9
Example 10
The conductive micro-foaming polypropylene material easy to spray, the reagents and the technological parameters used in each step are the same as those in the embodiment 2, except that the polar copolymer is polyvinyl chloride.
Example 11
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the polar copolymer is ethylene-methyl methacrylate copolymer.
Example 12
The conductive micro-foaming polypropylene material easy to spray is the same as the example 2 in each step, and the reagents and technological parameters used in each step, except that the azodicarbonamide foaming master batch is replaced by equivalent 4,4' -oxo-bis-benzenesulfonyl hydrazide.
Example 13
The conductive micro-foaming polypropylene material easy to spray, the reagents and the technological parameters used in each step are the same as those in the embodiment 2, except that the azodicarbonamide foaming master batch is replaced by sodium bicarbonate with the same amount.
Example 14
The conductive micro-foaming polypropylene material easy to spray is the same as that of the embodiment 2 in each step, and the reagents and the process parameters used in each step are the same, except that the carbon nano tube comprises a single-wall carbon nano tube and a multi-wall carbon nano tube in a mass ratio of 1:2.
Example 15
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the carbon nano tube comprises single-wall carbon nano tube and multi-wall carbon nano tube with the mass ratio of 0.5:2.
Comparative example 1
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that 25kg of conductive carbon black is adopted for replacing 5kg of carbon nano-tubes.
Comparative example 2
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that 5kg of carbon nano-tubes are replaced by 5kg of conductive carbon black.
Comparative example 3
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the addition amount of the polar copolymer is 0.
Comparative example 4
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the addition amount of the foaming agent is 0.
Comparative example 5
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the addition amount of the polar copolymer is 1kg.
Comparative example 6
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the addition amount of the polar copolymer is 15kg.
Comparative example 7
The conductive micro-foaming polypropylene material easy to spray, the reagents and the process parameters used in each step are the same as those in the embodiment 2, except that the addition amount of the carbon nano tube is 18kg.
Performance test
1. Density after foaming: the polypropylene materials of examples 1-15 and comparative examples 1-7 were tested according to the I SO 1183-2019 standard and the test results are shown in Table 4 in g/cm 3 。
2. Cantilever arm impact strength: the polypropylene materials of examples 1-15 and comparative examples 1-7 were tested according to the I SO 180-2019 standard at 25℃and the test results are shown in Table 4 in kJ/m 2 。
3. Surface resistance: the polypropylene materials of examples 1-15 and comparative examples 1-7 were tested according to ASTM D257-2014, with a PRS-801 surface resistance meter at 25℃and a relative humidity of 55%, and the test results are shown in Table 4.
4. The spraying effect is as follows: spraying plastic paint with the thickness of 20 μm; the polypropylene materials of examples 1-15 and comparative examples 1-7 were cross-cut according to ASTM D3359-87, with 0 being the optimum, the grade being shown in Table 3, and the test results being shown in Table 4.
TABLE 3 criteria for cross-hatch level test
TABLE 4 Performance test results for examples 1-15 and comparative examples 1-7
As can be seen from the performance detection results of the embodiment 2 and the comparative examples 1-2 in the table 4, the carbon nanotubes are adopted to provide the conductivity, meanwhile, the carbon nanotubes are uniformly dispersed in the system, the influence on foaming is small, the compatibility of the conductive carbon black in the system is poor, the dispersion is uneven, the conductivity of the conductive carbon black equal to the carbon nanotubes is insufficient, a large amount of conductive carbon black needs to be added to improve the conductivity, and more conductive carbon black is unevenly dispersed in the system, so that carbon powder particles fall off and the density is large on the surface of a product, the foaming effect is poor, the carbon nanotubes adopted in the application cannot influence the content increase and the carbon powder falls off, and the pollution caused when the material is applied to electronic dustproof equipment is avoided. The cross-cut grade of the spray detection of the finally obtained conductive foaming polypropylene material reaches more than 2 levels, and the density after foaming reaches less than 0.785 g/cm 3 The surface resistance is lower than E4, and the impact strength of the cantilever beam is higher than 10 kJ/m 2 。
As can be seen from the performance test results of example 2 and comparative example 4 in table 4, the foaming agent can provide the self foaming function of the polypropylene material, and even foaming cells can ensure uniform resistance, so that the effects of light weight and high conductivity are achieved, while the product of comparative example 4 cannot achieve the light weight effect.
As can be seen from the performance test results of example 2 and comparative examples 3 and 5-6 in Table 4, the polar copolymer added in the present application can improve the polarity of the polypropylene material, and the change of the polarity can enhance the adhesion between the ink and the surface, thereby achieving the effect of improving the spraying easiness; when the polar copolymer content is too low, a sufficient number of polar ink-philic areas cannot be formed on the surface, resulting in insufficient bonding force between the ink and the surface of the article. When the polar copolymer is too much, the compatibility with polypropylene is poor, so that the material is easy to delaminate, the defects such as peeling and the like are generated, and the impact is also poor.
As can be seen from the performance test results of examples 2 and 5 in Table 4, the white oil, polysiloxane and 2,2' -methylenebis (4, 6-di-tert-butylphenyl phosphate) basic aluminum added in the present application help to improve the dispersibility of the carbon nanotubes, and to maximize the conductivity of the material while ensuring that the densities of the products are not greatly different.
As can be seen from the performance test results of examples 2 and 6 in table 4, the lower melt strength of the polypropylene resin has an effect on foaming, and the lower melt strength can affect the foaming effect, so that the foaming of the product is uneven, the density is higher, the melt strength of the polypropylene resin is controlled to be higher than 30cN, the foaming effect can be ensured, and the lightweight performance can be improved.
As can be seen from the performance test results of examples 2 and 7-8 in Table 3, the compatibility of the carbon nanotubes and the polar copolymer with the polypropylene resin is preferably improved synchronously by grafting PE with maleic anhydride on the premise of ensuring that the mechanical properties of the impact strength are not greatly different, so that the foaming performance of the material is further effectively improved, and the light weight of the product is improved.
The foregoing embodiments have been provided for the purpose of illustrating the general principles of the present invention, and are not to be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art without departing from the spirit and principles of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The conductive micro-foaming polypropylene material easy to spray is characterized by comprising the following components in parts by weight:
polypropylene resin: 54-80 parts;
toughening agent: 12-20 parts;
carbon nanotubes: 0.5-10 parts;
polar copolymer: 3-11 parts;
foaming agent: 1-2 parts;
and (3) a compatilizer: 1-3 parts;
an antioxidant: 0.1 to 0.5 part;
wherein the polar copolymer is one or more of polyvinyl chloride, ethylene-acrylic ester-glycidyl methacrylate terpolymer and ethylene-methyl methacrylate copolymer.
2. The sprayable conductive micro-foaming polypropylene material of claim 1, wherein the compatilizer is one or more of maleic anhydride grafted PE, maleic anhydride grafted PP, 2-2-trimethoxysilylpropyl methyl silane, 3-glycidoxypropyl trimethoxysilane.
3. A sprayable electrically conductive micro-foamed polypropylene material according to claim 1, wherein said polypropylene resin has a melt strength of > 30cN under 190 ℃.
4. The sprayable conductive micro-foaming polypropylene material according to claim 1, wherein the foaming agent is one or more of azodicarbonamide, sodium bicarbonate, citric acid, sodium carbonate, ammonium carbonate, 4' -oxybis benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, dinitroso pentamethylene tetramine; the antioxidant is hindered phenol antioxidant and/or phosphite antioxidant.
5. The sprayable conductive micro-foaming polypropylene material of claim 1, further comprising 0.3 to 0.7 parts by weight of white oil, 0.1 to 0.5 parts by weight of 2,2' -methylenebis (4, 6-di-tert-butylphenyl phosphate) basic aluminum and 0.2 to 0.5 parts by weight of polysiloxane.
6. A sprayable electrically conductive micro-foamed polypropylene material according to claim 1 comprising at least one of the following (1) - (3):
(1) The polar copolymer is an ethylene-acrylic ester-glycidyl methacrylate terpolymer;
(2) The compatilizer is maleic anhydride grafted PE;
(3) The foaming agent is azodicarbonamide foaming agent or azodicarbonamide foaming master batch.
7. The conductive micro-foaming polypropylene material easy to spray according to claim 1, wherein the carbon nano tube comprises the following components in percentage by mass (0.8-1.5): 2 and multi-walled carbon nanotubes.
8. The sprayable electrically conductive micro-foamed polypropylene material of claim 1 wherein the toughening agent is one or more of an ethylene-octene copolymer, an ethylene-propylene-diene terpolymer, an ethylene propylene rubber, a styrene-butadiene thermoplastic elastomer, and an ethylene-vinyl acetate copolymer.
9. A method for preparing the easily sprayed conductive micro-foaming polypropylene material as claimed in any one of claims 1 to 8, comprising the following steps:
(1) Putting the components into a high-speed mixer, fully stirring, and uniformly mixing to obtain a premix;
(2) And (3) placing the premix into a main feeding port of double-screw extrusion equipment for melting, extruding, granulating and drying, wherein the melting extrusion temperature is 150-220 ℃, the main machine rotating speed is 300-600r/min, and the length-diameter ratio of the double-screw extruder is (10-50): 1, so that the conductive micro-foaming polypropylene material easy to spray is obtained.
10. Use of the easily sprayable conductive micro-foaming polypropylene material according to any one of claims 1-8 in the field of dust-proof packaging and antistatic transfer cases.
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