CN111518337A - Graphene/basalt fiber reinforced composite material and preparation method thereof - Google Patents
Graphene/basalt fiber reinforced composite material and preparation method thereof Download PDFInfo
- Publication number
- CN111518337A CN111518337A CN202010506692.2A CN202010506692A CN111518337A CN 111518337 A CN111518337 A CN 111518337A CN 202010506692 A CN202010506692 A CN 202010506692A CN 111518337 A CN111518337 A CN 111518337A
- Authority
- CN
- China
- Prior art keywords
- graphene
- basalt fiber
- parts
- composite material
- reinforced composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 248
- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 176
- 239000000463 material Substances 0.000 title claims abstract description 102
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 83
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims description 52
- 239000012745 toughening agent Substances 0.000 claims description 41
- 239000003607 modifier Substances 0.000 claims description 35
- 239000002270 dispersing agent Substances 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 28
- -1 polyethylene Polymers 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 5
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 230000017525 heat dissipation Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000011825 aerospace material Substances 0.000 abstract description 3
- 230000002093 peripheral effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 235000011837 pasties Nutrition 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007909 melt granulation Methods 0.000 description 6
- 125000005375 organosiloxane group Chemical group 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920006253 high performance fiber Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a graphene/basalt fiber reinforced composite material and a preparation method thereof, and relates to the technical field of composite materials, so that the graphene/basalt fiber reinforced composite material has the advantages of environmental protection, high temperature resistance and high heat dissipation performance. The graphene/basalt fiber reinforced composite material comprises: graphene dispersion, silanized basalt fibers and thermoplastic resin. The graphene/basalt fiber reinforced composite material provided by the invention is applied to household appliance heat dissipation parts, automobile engine peripheral materials and aerospace materials.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a graphene/basalt fiber reinforced composite material and a preparation method thereof.
Background
In recent years, people are attracting more and more attention to develop novel composite materials with the advantages of environmental protection, high temperature resistance and high heat dissipation by utilizing renewable resources. The basalt fiber has great potential advantages as a green, environment-friendly and recyclable high-performance fiber. However, basalt fibers have poor surface properties, are difficult to bundle and surface-modify, and have poor alkali resistance due to a large proportion of silica, and thus have poor applicability in the face of special environments.
Further, graphene has recently attracted attention as a high-performance novel material. However, due to the strong van der waals force between graphene sheets, aggregation is easily generated in the processing process, the graphene sheets with complete structures are in an inert state, the chemical stability is high, and the graphene sheets are difficult to be tightly combined with a polymer phase, so that the graphene is difficult to disperse in a polymer matrix by a processing process (particularly a melt mixing process), and the composite material prepared from the graphene and the basalt fiber cannot fully exert the functions of the composite material.
Disclosure of Invention
The invention aims to provide a graphene/basalt fiber reinforced composite material and a preparation method thereof, so that the graphene/basalt fiber reinforced composite material has an environment-friendly, high-temperature-resistant and high-heat-dissipation composite material.
In order to achieve the above object, the present invention provides a graphene/basalt fiber reinforced composite material, comprising: graphene dispersion, silanized basalt fibers and thermoplastic resin.
Compared with the prior art, in the graphene/basalt fiber reinforced composite material provided by the invention, graphene contained in the graphene dispersion not only has the performances of high temperature resistance, good thermal conductivity, chemical stability and the like, but also can exist in the form of the dispersion, so that strong van der waals force exists between sheets in a lamellar structure of the graphene, the silanized basalt fiber and the thermoplastic resin are not easy to aggregate during blending, and the prepared graphene/basalt fiber reinforced composite material is ensured to have good high temperature resistance and good heat dissipation performance. In addition, in the graphene/basalt fiber reinforced composite material provided by the invention, the silanized basalt fiber is easy to degrade, and the silanized basalt fiber is uniformly dispersed in the graphene/basalt fiber reinforced composite material, so that after the silanized basalt fiber is degraded, graphene and thermoplastic resin can be separated from a degradation product to regenerate the graphene/basalt fiber reinforced composite material. Meanwhile, the thermoplastic resin is used as a solvent of the graphene dispersoid and the silanized basalt fiber, so that the silanized basalt fiber and the graphene are supported. In addition, the silanized basalt fiber has good surface activity and interface binding force, so that the graphene dispersion, the silanized basalt fiber and the thermoplastic resin have good interface compatibility, the graphene dispersion, the silanized basalt fiber and the thermoplastic resin can be uniformly mixed, and the graphene/basalt fiber reinforced composite material is ensured to have stable high-temperature resistance and high heat dissipation function. Moreover, when silanized basalt fibers contained in the graphene/basalt fiber reinforced composite material are degraded, the obtained degradation product is not easy to form blocks, so that the graphene/basalt fiber reinforced composite material regenerated by the degradation product has good processing performance.
The invention also provides a preparation method of the graphene/basalt fiber reinforced composite material, which comprises the following steps:
at least uniformly mixing the graphene dispersoid and thermoplastic resin to obtain a mixture;
and adding the mixture into a main feeding port of an extruder in a forced feeding mode, and adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode to obtain the graphene/basalt fiber reinforced composite material.
Compared with the prior art, the preparation method of the graphene/basalt fiber reinforced composite material provided by the invention has the same beneficial effects as the graphene/basalt fiber reinforced composite material in the technical scheme, and the details are not repeated herein.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", and the like, indicate orientations or positional relationships and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The performance advantages of all aspects of plastic materials enable the application range of the plastic materials to be wider and wider, but most of the plastic materials are continuously increased due to nondegradable plastic wastes which are durable and non-corrosive, so that the inedible 'white revolution' is led to become the 'white wastes' which are headaches for mankind. In addition, while the demand of people for materials is continuously increased, the requirements for the performance and quality of the materials in various aspects in various industrial production are also continuously improved, the performance of a single material cannot meet the requirements, and the development and research of high-performance and environment-friendly composite materials become the key points in the field of new material development.
In recent years, the development of new composite materials using renewable resources has attracted more and more attention. The basalt fiber has great potential advantages as a green, environment-friendly and recyclable high-performance fiber. The basalt fiber has outstanding temperature resistance and good tensile strength, is rich in resources in nature, most importantly, can be naturally degraded, and is an environment-friendly product with excellent performance when being combined with a composite material prepared from thermoplastic resin.
Further, graphene has recently attracted attention as a high-performance novel material. Graphene, the thinnest material known in the world, is only one carbon atom thick, 0.335 nanometers thick, and is only 20 ten-thousandths of hair; the strength of the nano material with high strength and strongest strength can reach 1000GPa, which is 200 times of that of steel and harder than diamond; the light transmittance is high, the visible light transmittance is as high as 97.7% (each layer only absorbs 2.3%), and the film is almost completely transparent; the specific surface area is large, up to 2630m2/g, which is twice of that of single-wall carbon nanotube. Graphene is the thinnest, the largest in strength and the strongest novel nano material in the world at present, and is called as 'black gold', which is the king of new materials. However, due to the strong van der waals force between graphene sheets, aggregation is easily generated during the processing, the graphene sheet with a complete structure is in an inert state, the chemical stability is high, tight combination with a polymer phase is difficult to realize, and graphene is difficult to disperse in a polymer matrix by a processing process (particularly a melt mixing process).
The graphene/basalt fiber reinforced composite material provided by the embodiment of the invention comprises: graphene dispersion, silanized basalt fibers and thermoplastic resin.
In specific implementation, the graphene dispersion, the silanized basalt fiber and the thermoplastic resin are mixed to obtain the graphene/basalt fiber reinforced composite material.
According to the specific implementation process, the graphene/basalt fiber reinforced composite material provided by the invention overcomes the defects of poor surface performance of basalt fibers and easy aggregation of graphene by mixing the graphene dispersoid, the silanized basalt fibers and the thermoplastic resin, and uses the thermoplastic resin as a solvent of the graphene dispersoid and the silanized basalt fibers to enable the graphene dispersoid and the silanized basalt fibers to be compatible, so that the graphene/basalt fiber reinforced composite material with the advantages of environmental protection, reproducibility, high temperature resistance and high heat dissipation is prepared.
Illustratively, the graphene dispersion is paste graphene slurry in which the graphene dispersion treatment is performed by using a graphene dispersant and water, and the graphene mass percentage is 4%. Wherein the weight ratio of the graphene dispersing agent to the graphene is (1-6): (1-6). According to the method, the graphene dispersing agent and water are selected to disperse the graphene, and the treated graphene dispersion is used as a base material, so that the defect that the graphene is easy to aggregate in the processing process is overcome, and the graphene can be better compatible with the silanized basalt fiber in the processing process. It should be understood that the graphene dispersing effect can be improved by the ratio of the graphene dispersing agent to graphene.
It is noted that the graphene dispersant is one or two of a silane coupling agent and sodium dodecyl sulfate. The silane coupling agent may be one or a combination of two or more of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, trimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, and gamma-aminopropyltrimethoxysilane. Specifically, the graphene dispersant may be a silane coupling agent, may also be sodium dodecyl sulfate, or may also be a mixture of a silane coupling agent and sodium dodecyl sulfate.
Illustratively, the silanized basalt fiber is a basalt fiber subjected to surface treatment with an aqueous solution of a silane coupling agent. The mass percentage of the silane coupling agent aqueous solution is 0.5-2%. The method selects the silane coupling agent aqueous solution to perform surfacing treatment on the basalt fiber, and the basalt fiber subjected to surfacing treatment has good interface compatibility with thermoplastic resin, so that the interface bonding force can be improved, and the mechanical property of the graphene/basalt fiber composite material is further improved.
Illustratively, the thermoplastic resin is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, and acrylonitrile-styrene-butadiene copolymer. Specifically, the thermoplastic resin may be polyethylene, polypropylene, or other combinations, which are not specifically listed.
Illustratively, the thermoplastic resin is one or more of polyethylene having a molecular weight of 20 to 60 ten thousand, polypropylene having a molecular weight of 3000 to 5000, polyvinyl chloride having a molecular weight of 5 to 11 ten thousand, polystyrene having a molecular weight of 18 to 22 ten thousand, and acrylonitrile-styrene-butadiene copolymer having a molecular weight of 15 to 30 ten thousand. The thermoplastic resin with the specific molecular weight is used as a solvent of graphene and basalt fibers, has lower surface tension than other thermoplastic resins with the specific molecular weight, and is more favorable for being compatible with the graphene and basalt fibers. The composite material prepared by using the thermoplastic resin and the silanized basalt fiber has the characteristics of degradability and environmental friendliness.
In some embodiments, the graphene/basalt fiber reinforced composite described above further comprises a modifying filler, a toughening agent, a compatibilizing agent, and a flow modifier. Wherein the modified filler comprises surface-active silica and/or surface-active treated calcium carbonate. It is to be understood that the modified filler herein may be surface-activated silica, surface-activated calcium carbonate, surface-activated silica and surface-activated calcium carbonate. The modified filler has good compatibility with thermoplastic resin, graphene and silanized basalt fiber, and has the characteristics of good hardness, good wear resistance and high temperature resistance. From the above, the thermoplastic resin, the graphene, the silanized basalt fiber and the modified filler interact with each other, so that the compatibility of each component of the composite material can be improved, and the heat resistance, the rigidity and the impact resistance of the composite material can be improved to the greatest extent.
The modified filler is modified by treating the modified filler with a surfactant, wherein the surfactant is oleic acid or sodium stearate, and the weight of the surfactant is 2-4 wt% of the weight of the modified filler. The surface tension of the modified filler activated by oleic acid or sodium stearate is reduced, so that the modified filler is more compatible with graphene, silanized basalt fiber and thermoplastic resin, and the dispersibility and compatibility of the modified filler are greatly improved.
The toughening agent is an acrylate copolymer with a core-shell structure. The acrylate copolymer with the core-shell structure takes an organic siloxane-acrylate composite rubber phase as a core and takes a methyl methacrylate-glycidyl methacrylate copolymer as a shell. The problem of poor toughness of the composite material caused by the addition of the silanized basalt fiber is further solved by adding the toughening agent with the core-shell structure.
The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The compatilizer has the functions of compatibilization and toughening in a composite material system, enhances the interface combination of hydrophilic modified graphene/basalt fiber and hydrophobic polymer thermoplastic resin, effectively improves the compatibility of the modified graphene, silanized basalt fiber and a thermoplastic resin matrix, and improves the comprehensive mechanical property of the composite material. The compatilizer can also generate energy dissipation, improve the effective transmission of stress, enhance the interface adhesion of graphene, silanized basalt fiber and a matrix, and further improve the impact strength, the toughness and the like of the composite material. The compatilizer is added to effectively improve the compatibility of the modified graphene, the silanized basalt fiber and the thermoplastic resin matrix, and the comprehensive performance of the composite material is improved.
The flow modifier is one or more of N, N' -ethylene bisstearamide, butyl stearate, oleamide and microcrystalline paraffin. According to the invention, the fluidity of the graphene and the silanized basalt fiber in the thermoplastic resin matrix can be further improved by adding the flow modifier, so that the graphene and the silanized basalt fiber are more uniformly fused, and the mechanical property of the composite material is further improved.
It can be understood that, the graphene/basalt fiber reinforced composite material comprises the following components in parts by weight: 1-6 parts of graphene, 1-6 parts of graphene dispersant, 10-25 parts of silanized basalt fiber, 45-75 parts of thermoplastic resin, 4-8 parts of modified filler, 6-12 parts of toughening agent, 2-5 parts of compatilizer and 0.1-1 part of flow modifier.
It can be understood that, the graphene/basalt fiber reinforced composite material comprises the following components in parts by weight: 2 to 5 parts of graphene, 2 to 5 parts of graphene dispersant, 15 to 20 parts of silanized basalt fiber, 50 to 65 parts of thermoplastic resin, 5 to 8 parts of modified filler, 8 to 10 parts of toughening agent, 3 to 5 parts of compatilizer and 0.1 to 1 part of flow modifier.
The invention provides a graphene/basalt fiber reinforced composite material which is prepared by taking thermoplastic resin, graphene and basalt fiber as base materials, performing dispersion treatment on the graphene, performing proper proportion on the graphene, a graphene dispersing agent and water, reasonably and uniformly dispersing the graphene into the water to obtain pasty graphene slurry with the graphene content of 4%, performing surface treatment on the basalt fiber by using 0.5-2% of silane coupling agent aqueous solution, and adding proper amount of modified filler, toughening agent, compatilizer and flow modifier. The composite material can be widely applied to the fields of household appliance heat dissipation parts, automobile engine peripheral materials and aerospace materials.
The embodiment of the invention also provides a preparation method of the graphene/basalt fiber reinforced composite material, which comprises the following steps: and at least uniformly mixing the graphene dispersion and the thermoplastic resin to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, and adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode to obtain the graphene/basalt fiber reinforced composite material. The extruder may be a twin-screw extruder. The distance between the side feeding port of the double-screw extruder and the machine head is 0.5-0.75 time of the distance between the main feeding port of the double-screw extruder and the machine head. When the distance between the feeding position of the silanized basalt fiber and the machine head is too long, the silanized basalt fiber is more easily subjected to long-time shearing damage to cause the length to be shortened, and the mechanical property of the product is poor. If the distance between the side feeding port and the machine head is 1/2-3/4 times of the distance between the main feeding port and the machine head, the best mixing effect can be achieved, and the silanized basalt fiber cannot be too short.
Compared with the prior art, the preparation method of the graphene/basalt fiber reinforced composite material provided by the invention has the same beneficial effects as the graphene/basalt fiber reinforced composite material, and is not repeated herein.
Specifically, before at least uniformly mixing the graphene dispersion and the thermoplastic resin to obtain a mixture, the preparation method further comprises:
the thermoplastic resin is subjected to a drying treatment. The drying temperature is 80-100 ℃, and the drying time is 4-6 hours.
Uniformly dispersing graphene and a graphene dispersing agent into water by using a planetary ball mill to obtain a graphene dispersion body.
Specifically, the mixing of at least the graphene dispersion and the thermoplastic resin to obtain a mixture includes:
stirring the graphene dispersoid, the thermoplastic resin, the modified filler, the toughening agent, the compatilizer and the flow modifier at the speed of 1000 r/min-1500 r/min for 1 minute-3 minutes, and then stirring at the speed of 500 r/min-1000 r/min for 1 minute-3 minutes to obtain a mixture.
Specifically, the heating temperature of the extruder is 170-210 ℃, and the extrusion temperature of the extruder head is 180-200 ℃. The rotating speed of a main machine screw of the extruder is 200 r/min-300 r/min, and the feeding rotating speed is 20 r/min-30 r/min. The rotating speed of a main machine screw of the extruder cannot be too high, if the rotating speed is higher, the shearing force is higher, the length of the silanized basalt fiber is shorter, the strength is reduced, and 200-300 r/min is a proper rotating speed range. Under the condition of full mixing, the rotating speed is controlled, the damage of high-speed shearing action on the silanized bamboo basalt fiber is effectively reduced, and the graphene/basalt fiber reinforced thermoplastic resin composite material with higher strength and toughness, good processability and appearance effect is prepared. Because the processing characteristics of the thermoplastic resin, the graphene dispersing agent, the silanized basalt fiber, the modified filler, the toughening agent, the compatilizer and the flow modifier composite material fluctuate with the temperature, in order to ensure the quality requirements of material mixing and molding, the conditions of heating temperature, machine head temperature, molding injection molding temperature, processing time and the like need to be optimized and strictly and reasonably managed.
The present invention provides a glass fiber reinforced polycarbonate composite material and a method for preparing the same, which are described in detail below with reference to the following examples, which are provided for illustration of the present invention and are not intended to be limiting. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The graphene/basalt fiber reinforced composite material in the embodiment comprises the following components in parts by weight: 55 parts of thermoplastic resin, 2.5 parts of graphene dispersant, 20 parts of silanized basalt fiber, 6 parts of modified filler, 9 parts of toughening agent, 4 parts of compatilizer and 0.3 part of flow modifier, and the formula is shown in Table 1.
The graphene is enhanced graphene (model SE1430), the graphene dispersing agent is a silane coupling agent, and the model is KH 560. The thermoplastic resin is polypropylene with the molecular weight of 3000-5000. The modified filler is surface active calcium carbonate, and the particle size of the modified filler is 200-500 nm. The toughening agent is an acrylate copolymer taking an organosiloxane-acrylate composite rubber phase as a core and a methyl methacrylate-glycidyl methacrylate copolymer as a shell, the weight ratio of acrylate to organosiloxane is 2:1, and the average particle size of the toughening agent is 250-350 nm. The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The flow modifier is N, N' -ethylene distearamide. The silanized basalt fiber is prepared by performing surface treatment on a silane coupling agent aqueous solution with the mass percent of 0.5%.
The preparation method of the graphene/basalt fiber reinforced composite material provided by the embodiment comprises the following steps:
55 parts of polypropylene resin with the molecular weight of 3000-5000 is dried at 80 ℃ for 4 hours.
Uniformly dispersing 2.5 parts of graphene and 2.5 parts of silane coupling agent into water by using a planetary ball mill to prepare pasty graphene slurry with the graphene content of 4%, namely graphene dispersoid.
And sequentially adding 55 parts of polypropylene resin with the molecular weight of 3000-5000, graphene dispersion, 6 parts of modified filler, 9 parts of toughening agent, 4 parts of compatilizer and 0.3 part of flowing modifier into blending equipment after drying treatment, stirring for 3 minutes at the speed of 1000r/min, and stirring for 1 minute at the speed of 500r/min to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode, and carrying out melt granulation to obtain the graphene/basalt fiber reinforced composite material. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
The extruder is a twin-screw extruder. The heating temperature of the double-screw extruder is 170-210 ℃, 1 section/170 ℃, 2 section/180 ℃,3 section/190 ℃, 4 section/200 ℃, 5 section/210 ℃, 6 section/210 ℃, 7 section/200 ℃, 8 section/200 ℃ and 9 section/195 ℃. The head extrusion temperature was 195 ℃. The screw rotating speed of a main machine of the double-screw extruder is 280r/min, and the feeding rotating speed is 25 r/min. The distance between the side feeding port of the double-screw extruder and the machine head is 0.65 times of the distance between the main feeding port and the machine head.
Example 2
The graphene/basalt fiber reinforced composite material in the embodiment comprises the following components in parts by weight: 60 parts of thermoplastic resin, 5 parts of graphene dispersant, 18 parts of silanized basalt fiber, 4 parts of modified filler, 6 parts of toughening agent, 2 parts of compatilizer and 0.1 part of flow modifier, wherein the proportions are shown in Table 1.
The graphene is enhanced graphene (model SE1430), the graphene dispersing agent is a silane coupling agent, and the model is KH 560. The thermoplastic resin is polyethylene, polypropylene, polyvinyl chloride, polystyrene and acrylonitrile-styrene-butadiene, and the mass ratio of the components is 1:1:1:1: 1. The molecular weight of the polyethylene is 20-60 ten thousand, the molecular weight of the polypropylene is 3000-5000, the molecular weight of the polyvinyl chloride is 5-11 ten thousand, the molecular weight of the polystyrene is 18-22 ten thousand, and the molecular weight of the acrylonitrile-styrene-butadiene copolymer is 15-30 ten thousand. The modified filler is surface active calcium carbonate and surface active silicon dioxide, the mass ratio of the components is 1:1, and the particle size of the modified filler is 200 nm-500 nm. The toughening agent is an acrylate copolymer taking an organosiloxane-acrylate composite rubber phase as a core and a methyl methacrylate-glycidyl methacrylate copolymer as a shell, the weight ratio of acrylate to organosiloxane is 3:1, and the average particle size of the toughening agent is 250-350 nm. The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The flow modifier is N, N' -ethylene bisstearamide, butyl stearate, oleamide and microcrystalline paraffin, and the mass ratio of the components is 1:1:1: 1. The silanized basalt fiber is prepared by performing surface treatment on a silane coupling agent aqueous solution with the mass percent of 2%.
The preparation method of the graphene/basalt fiber reinforced composite material provided by the embodiment comprises the following steps:
60 parts of thermoplastic resin is dried at 80 ℃ for 4 hours.
Uniformly dispersing 5 parts of graphene and 5 parts of silane coupling agent into water by using a planetary ball mill to prepare pasty graphene slurry with the graphene content of 4%, namely graphene dispersoid.
And sequentially adding 60 parts of dried thermoplastic resin, the graphene dispersion, 4 parts of modified filler, 6 parts of toughening agent, 2 parts of compatilizer and 0.1 part of flow modifier into blending equipment, stirring for 3 minutes at the speed of 1000r/min, and stirring for 3 minutes at the speed of 500r/min to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode, and carrying out melt granulation to obtain the graphene/basalt fiber reinforced composite material. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
The extruder is a twin-screw extruder. The heating temperature of the double-screw extruder is 170-210 ℃, 1 section/170 ℃, 2 section/180 ℃,3 section/190 ℃, 4 section/200 ℃, 5 section/210 ℃, 6 section/210 ℃, 7 section/200 ℃, 8 section/200 ℃ and 9 section/195 ℃. The head extrusion temperature was 180 ℃. The main machine screw rotating speed of the double-screw extruder is 250r/min, and the feeding rotating speed is 20 r/min. The distance between the side feeding port of the double-screw extruder and the machine head is 0.5 times of the distance between the main feeding port and the machine head.
Example 3
The graphene/basalt fiber reinforced composite material in the embodiment comprises the following components in parts by weight: 57 parts of thermoplastic resin, 3 parts of graphene dispersant, 15 parts of silanized basalt fiber, 8 parts of modified filler, 8 parts of toughening agent, 5 parts of compatilizer and 0.3 part of flow modifier, and the proportion is shown in Table 1.
The graphene is enhanced graphene (model SE1430), and the graphene dispersing agent is sodium dodecyl sulfate. The thermoplastic resin is polyethylene, polypropylene and polyvinyl chloride, and the mass ratio of the components is 1:1: 1. The molecular weight of the polyethylene is 20-60 ten thousand, the molecular weight of the polypropylene is 3000-5000, and the molecular weight of the polyvinyl chloride is 5-11 ten thousand. The modified filler is surface active silicon dioxide, and the particle size of the modified filler is 200-500 nm. The toughening agent is an acrylate copolymer which takes an organosiloxane-acrylate composite rubber phase as a core and takes a methyl methacrylate-glycidyl methacrylate copolymer as a shell, the weight ratio of acrylate to organosiloxane is 1:1, and the average particle size of the toughening agent is 250-350 nm. The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The flow modifier is butyl stearate, oleamide and microcrystalline wax, and the mass ratio of the components is 1:1: 1. The silanized basalt fiber is prepared by performing surface treatment on a 1% silane coupling agent aqueous solution by mass percent.
The preparation method of the graphene/basalt fiber reinforced composite material provided by the embodiment comprises the following steps:
57 parts of a thermoplastic resin was dried at 85 ℃ for 4 hours.
Uniformly dispersing 3 parts of graphene and 3 parts of silane coupling agent into water by using a planetary ball mill to prepare pasty graphene slurry with the graphene content of 4%, namely graphene dispersoid.
And sequentially adding 57 parts of dried thermoplastic resin, the graphene dispersion, 8 parts of modified filler, 8 parts of toughening agent, 5 parts of compatilizer and 0.3 part of flow modifier into blending equipment, stirring at the speed of 1200r/min for 2 minutes, and then stirring at the speed of 800r/min for 2 minutes to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, adding 15 parts of silanized basalt fiber into a side feeding port of the extruder in a side feeding mode, and carrying out melt granulation to obtain the graphene/basalt fiber reinforced composite material. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
The extruder is a twin-screw extruder. The heating temperature of the double-screw extruder is 170-210 ℃, 1 section/170 ℃, 2 section/180 ℃,3 section/190 ℃, 4 section/200 ℃, 5 section/210 ℃, 6 section/210 ℃, 7 section/200 ℃, 8 section/200 ℃ and 9 section/195 ℃. The head extrusion temperature was 200 ℃. The screw rotating speed of a main machine of the double-screw extruder is 300r/min, and the feeding rotating speed is 25 r/min. The distance between the side feeding port of the double-screw extruder and the machine head is 0.65 times of the distance between the main feeding port and the machine head.
Example 4
The graphene/basalt fiber reinforced composite material in the embodiment comprises the following components in parts by weight: 50 parts of thermoplastic resin, 4 parts of graphene dispersant, 20 parts of silanized basalt fiber, 7 parts of modified filler, 10 parts of toughening agent, 4.5 parts of compatilizer and 0.5 part of flow modifier, and the proportion is shown in Table 1.
The graphene is enhanced graphene (model SE1430), the graphene dispersing agent is a silane coupling agent, and the model is KH 560. Sodium lauryl sulfate. The thermoplastic resin is polyethylene having a molecular weight of 20 to 60 ten thousand. The modified filler is surface active silicon dioxide, and the particle size of the modified filler is 200 nm-500 nm. The toughening agent is an acrylate copolymer which takes an organosiloxane-acrylate composite rubber phase as a core and takes a methyl methacrylate-glycidyl methacrylate copolymer as a shell, the weight ratio of the acrylate to the organosiloxane is 1.5:1, and the average particle size of the toughening agent is 250 nm-350 nm. The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The flow modifier is microcrystalline paraffin. The silanized basalt fiber is prepared by performing surface treatment on 1.5 mass percent of silane coupling agent aqueous solution.
The preparation method of the graphene/basalt fiber reinforced composite material provided by the embodiment comprises the following steps:
50 parts of thermoplastic resin is dried at 80 ℃ for 4 hours.
Uniformly dispersing 4 parts of graphene and 4 parts of silane coupling agent into water by using a planetary ball mill to prepare pasty graphene slurry with the graphene content of 4%, namely graphene dispersoid.
And sequentially adding 50 parts of dried thermoplastic resin, the graphene dispersion, 7 parts of modified filler, 10 parts of toughening agent, 4.5 parts of compatilizer and 0.5 part of flowing modifier into blending equipment, stirring at the speed of 1500r/min for 1 minute, and stirring at the speed of 500r/min for 3 minutes to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode, and carrying out melt granulation to obtain the graphene/basalt fiber reinforced composite material. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
The extruder is a twin-screw extruder. The heating temperature of the double-screw extruder is 170-210 ℃, 1 section/170 ℃, 2 section/180 ℃,3 section/190 ℃, 4 section/200 ℃, 5 section/210 ℃, 6 section/210 ℃, 7 section/200 ℃, 8 section/200 ℃ and 9 section/195 ℃. The head extrusion temperature was 200 ℃. The screw rotating speed of a main machine of the double-screw extruder is 280r/min, and the feeding rotating speed is 27 r/min. The distance between the side feeding port of the double-screw extruder and the machine head is 0.7 times of the distance between the main feeding port and the machine head.
Example 5
The graphene/basalt fiber reinforced composite material in the embodiment comprises the following components in parts by weight: 45 parts of thermoplastic resin, 1 part of graphene dispersant, 10 parts of silanized basalt fiber, 4 parts of modified filler, 6 parts of toughening agent, 2 parts of compatilizer and 0.1 part of flow modifier, and the proportion is shown in Table 1.
The graphene is enhanced graphene (model SE1430), the graphene dispersing agent is a silane coupling agent, and the model is KH 560. The thermoplastic resin is polyvinyl chloride, polystyrene and acrylonitrile-styrene-butadiene copolymer, and the mass ratio of the components is 1:1: 1. wherein the molecular weight of the polyvinyl chloride is 5-11 ten thousand, the molecular weight of the polystyrene is 18-22 ten thousand, and the molecular weight of the acrylonitrile-styrene-butadiene copolymer is 15-30 ten thousand. The modified filler is surface active calcium carbonate, and the particle size of the modified filler is 200 nm-500 nm. The toughening agent is an acrylate copolymer which takes an organosiloxane-acrylate composite rubber phase as a core and takes a methyl methacrylate-glycidyl methacrylate copolymer as a shell, the weight ratio of the acrylate to the organosiloxane is 2:1, and the average particle size of the toughening agent is 250 nm-350 nm. The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The flow modifier is N, N' -ethylene distearamide. The silanized basalt fiber is prepared by performing surface treatment on a silane coupling agent aqueous solution with the mass percent of 0.5%.
The preparation method of the graphene/basalt fiber reinforced composite material provided by the embodiment comprises the following steps:
45 parts of a thermoplastic resin was dried at 90 ℃ for 5 hours.
Uniformly dispersing 1 part of graphene and 1 part of silane coupling agent into water by using a planetary ball mill to prepare pasty graphene slurry with the graphene content of 4%, namely graphene dispersoid.
And sequentially adding 45 parts of dried thermoplastic resin, the graphene dispersion, 4 parts of modified filler, 6 parts of toughening agent, 2 parts of compatilizer and 0.1 part of flow modifier into blending equipment, stirring at the speed of 1100r/min for 2 minutes, and then stirring at the speed of 510r/min for 2 minutes to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode, and carrying out melt granulation to obtain the graphene/basalt fiber reinforced composite material. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
The extruder is a twin-screw extruder. The heating temperature of the double-screw extruder is 170-210 ℃, 1 section/170 ℃, 2 section/180 ℃,3 section/190 ℃, 4 section/200 ℃, 5 section/210 ℃, 6 section/210 ℃, 7 section/200 ℃, 8 section/200 ℃ and 9 section/195 ℃. The head extrusion temperature was 185 ℃. The main machine screw rotating speed of the double-screw extruder is 200r/min, and the feeding rotating speed is 20 r/min. The distance between the side feeding port of the double-screw extruder and the machine head is 0.6 times of the distance between the main feeding port and the machine head.
Example 6
The graphene/basalt fiber reinforced composite material in the embodiment comprises the following components in parts by weight: 75 parts of thermoplastic resin, 6 parts of graphene dispersant, 25 parts of silanized basalt fiber, 5 parts of modified filler, 12 parts of toughening agent, 3 parts of compatilizer and 0.7 part of flow modifier, wherein the proportion is shown in Table 1.
The graphene is enhanced graphene (model SE1430), and the graphene dispersing agent is sodium dodecyl sulfate. The thermoplastic resin is polyethylene and polypropylene, and the mass ratio of the components is 1: 1. The molecular weight of the polyethylene is 20-60 ten thousand, and the molecular weight of the polypropylene is 3000-5000. The modified filler is calcium carbonate with surface activity treatment, and the particle size of the modified filler is 200 nm-500 nm. The toughening agent is an acrylate copolymer which takes an organosiloxane-acrylate composite rubber phase as a core and takes a methyl methacrylate-glycidyl methacrylate copolymer as a shell, the weight ratio of acrylate to organosiloxane is 1:1, and the average particle size of the toughening agent is 250-350 nm. The compatilizer is maleic anhydride grafted ethylene-octene copolymer. The flow modifier is N, N' -ethylene bisstearamide, butyl stearate, oleamide and microcrystalline paraffin, and the mass ratio of the components is 1:1:1: 1. The silanized basalt fiber is prepared by performing surface treatment on a 1% silane coupling agent aqueous solution by mass percent.
The preparation method of the graphene/basalt fiber reinforced composite material provided by the embodiment comprises the following steps:
75 parts of thermoplastic resin is dried at 100 ℃ for 6 hours.
Uniformly dispersing 6 parts of graphene and 6 parts of silane coupling agent into water by using a planetary ball mill to prepare pasty graphene slurry with the graphene content of 4%, namely graphene dispersoid.
And sequentially adding 75 parts of dried thermoplastic resin, the graphene dispersion, 5 parts of modified filler, 12 parts of toughening agent, 3 parts of compatilizer and 0.7 part of flow modifier into blending equipment, stirring at the speed of 1200r/min for 2 minutes, and then stirring at the speed of 800r/min for 2 minutes to obtain a mixture.
And adding the mixture into a main feeding port of an extruder in a forced feeding mode, adding 15 parts of silanized basalt fiber into a side feeding port of the extruder in a side feeding mode, and carrying out melt granulation to obtain the graphene/basalt fiber reinforced composite material. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
The extruder is a twin-screw extruder. The heating temperature of the double-screw extruder is 170-210 ℃, 1 section/170 ℃, 2 section/180 ℃,3 section/190 ℃, 4 section/200 ℃, 5 section/210 ℃, 6 section/210 ℃, 7 section/200 ℃, 8 section/200 ℃ and 9 section/195 ℃. The head extrusion temperature was 190 ℃. The screw rotating speed of a main machine of the double-screw extruder is 260r/min, and the feeding rotating speed is 30 r/min. The distance between the side feeding port of the double-screw extruder and the machine head is 0.75 times of the distance between the main feeding port and the machine head.
Comparative example 1
The graphene/basalt fiber reinforced composite material in the comparative example is basically the same as that in example 1, and only the component proportions are different. The components in the comparative example are as follows according to parts by weight: 70 parts of thermoplastic resin, 2.5 parts of graphene dispersant, 5 parts of silanized basalt fiber, 6 parts of modified filler, 9 parts of toughening agent, 4 parts of compatilizer and 0.3 part of flow modifier, and the formula is shown in Table 1.
The preparation method of the graphene/basalt fiber reinforced composite material of the comparative example is the same as that of example 1. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
Comparative example 2
The graphene/basalt fiber reinforced composite material in the comparative example is as follows: the modified filler of example 1 was removed and its weight components were added to the thermoplastic resin without changing the weight of other components.
The preparation method of the graphene/basalt fiber reinforced composite material of the comparative example is the same as that of example 1. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
Comparative example 3
The graphene/basalt fiber reinforced composite material in the comparative example is basically the same as that in example 2, and the difference is that: the molecular weight of the polyethylene is 1-10 ten thousand, the molecular weight of the polypropylene is 1000-8000, the molecular weight of the polyvinyl chloride is 1-20 ten thousand, the molecular weight of the polystyrene is 2-16 ten thousand, and the molecular weight of the acrylonitrile-styrene-butadiene copolymer is 10-50 ten thousand.
The preparation method of the graphene/basalt fiber reinforced composite material of the comparative example is the same as that of example 2. The obtained graphene/basalt fiber reinforced composite material and the preparation performance thereof are shown in table 2.
TABLE 1 graphene/basalt fiber reinforced composite material and raw materials and mixture ratio for preparing the same
Unit: wt.%
TABLE 2 graphene/basalt fiber reinforced composite material and preparation performance thereof
In the above examples, tensile strength and elongation at break were measured according to the national standard GB/T1040.2-2006 and flexural strength and flexural modulus were measured according to the national standard GB/T9341-2000. The notched Izod impact strength was tested according to the national standard GB/T1843-2008. The melt flow rate was tested according to the national standard GB/T3682-2000.
As can be seen from tables 1 and 2, the graphene/basalt fiber reinforced composite material prepared by the components and the preparation method of the embodiments 1 to 6 of the invention has good mechanical properties and mechanical properties.
In addition, by comparing comparative example 1 with examples 1 to 6 of the present invention, it can be understood that the content of basalt fiber in comparative example 1 is not within the limit range of the present invention, the mechanical properties (tensile strength, flexural strength, notched impact strength) of the composite material are poor, and the application thereof in many fields is limited.
By comparing comparative example 2 with examples 1 to 6 of the present invention, it can be seen that the comparative example 2 has poor mechanical properties due to the absence of the modified filler, and the composite material has poor strength and toughness and is limited in practical application.
By comparing comparative example 3 with the examples of the present invention, it can be seen that since the thermoplastic resin in comparative example 3 is not the thermoplastic resin having the molecular weight defined in the present invention, the compatibility of the graphene and basalt fiber with the matrix thermoplastic resin and other components is poor, the mechanical properties of the composite material are insufficient, and practical applications are limited.
From the above, the invention provides the environment-friendly high-temperature-resistant graphene/basalt fiber reinforced composite material prepared by using the thermoplastic resin, the graphene and the basalt fiber as the base materials, performing dispersion treatment on the graphene to obtain pasty graphene slurry with the graphene content of 4%, performing surface treatment on the basalt fiber by using 0.5-2% of silane coupling agent aqueous solution, and adding a proper amount of modified filler, toughening agent, compatilizer and flow modifier. By adding the modified filler, the thermoplastic resin, the graphene, the silanized basalt fiber and the modified filler are interacted, so that the compatibility of each component of the composite material can be improved, and the heat resistance, the rigidity and the impact resistance of the composite material can be improved to the greatest extent. The problem of poor toughness of the composite material caused by the addition of the silanized basalt fiber is further solved by adding the toughening agent with the core-shell structure. The compatibility of the modified graphene, the basalt fiber and the thermoplastic resin matrix is effectively improved by adding the compatilizer, and the comprehensive performance of the composite material is improved. By adding the flow modifier, the fluidity of the graphene and the silanized basalt fiber in the thermoplastic resin matrix can be further improved, the graphene and the silanized basalt fiber can be more uniformly fused, and the mechanical property of the composite material can be further improved.
The compatibility of the graphene and basalt fibers with the thermoplastic resin can be improved through the specific component proportion of the graphene/basalt fiber reinforced composite material, so that the dispersibility and the solution fluidity of the graphene and basalt fibers in the thermoplastic resin matrix are improved, the graphene and basalt fibers and the thermoplastic resin can be effectively fused, the reinforcing effect of the graphene and basalt fibers on the thermoplastic resin is further improved, and the mechanical property of the composite material is improved. The composite material can be widely applied to the fields of household appliance heat dissipation parts, automobile engine peripheral materials and aerospace materials.
In the aspect of material processing, the thermoplastic resin, the graphene dispersant, the basalt fiber, the modified filler, the toughening agent, the compatilizer and the flow modifier are mixed by adopting but not limited to an extrusion process, and the material is formed by adopting but not limited to an injection molding process.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A graphene/basalt fiber reinforced composite material is characterized by comprising: graphene dispersion, silanized basalt fibers and thermoplastic resin.
2. The graphene/basalt fiber reinforced composite material according to claim 1, wherein the graphene dispersion is a paste graphene slurry in which graphene is dispersed with a graphene dispersant and water at a graphene mass percentage of 4%; wherein the content of the first and second substances,
the weight ratio of the graphene dispersing agent to the graphene is (1-6): (1-6); and/or the presence of a gas in the gas,
the graphene dispersing agent is one or two of a silane coupling agent and sodium dodecyl sulfate.
3. The graphene/basalt fiber-reinforced composite material according to claim 1, wherein the silanized basalt fiber is a basalt fiber subjected to surface treatment with a silane coupling agent aqueous solution; the mass percentage of the silane coupling agent aqueous solution is 0.5-2%.
4. The graphene/basalt fiber-reinforced composite according to claim 1, wherein the thermoplastic resin is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, and acrylonitrile-styrene-butadiene copolymer; or the like, or, alternatively,
the thermoplastic resin is one or more of polyethylene with the molecular weight of 20-60 ten thousand, polypropylene with the molecular weight of 3000-5000, polyvinyl chloride with the molecular weight of 5-11 ten thousand, polystyrene with the molecular weight of 18-22 ten thousand and acrylonitrile-styrene-butadiene copolymer with the molecular weight of 15-30 ten thousand.
5. The graphene/basalt fiber-reinforced composite according to claim 1, further comprising: modified fillers, toughening agents, compatibilizers and flow modifiers; wherein the modified filler comprises surface-active silica and/or surface-active treated calcium carbonate; and/or the presence of a gas in the gas,
the toughening agent is an acrylate copolymer with a core-shell structure; the acrylate copolymer with the core-shell structure takes an organosiloxane-acrylate composite rubber phase as a core and takes a methyl methacrylate-glycidyl methacrylate copolymer as a shell; and/or the presence of a gas in the gas,
the compatilizer is maleic anhydride grafted ethylene-octene copolymer; and/or the presence of a gas in the gas,
the flow modifier is one or more of N, N' -ethylene bisstearamide, butyl stearate, oleamide and microcrystalline paraffin.
6. The graphene/basalt fiber reinforced composite according to any of claims 1 to 5, wherein the graphene/basalt fiber reinforced composite comprises, in parts by weight: 1-6 parts of graphene, 1-6 parts of graphene dispersant, 10-25 parts of silanized basalt fiber, 45-75 parts of thermoplastic resin, 4-8 parts of modified filler, 6-12 parts of toughening agent, 2-5 parts of compatilizer and 0.1-1 part of flow modifier; or the like, or, alternatively,
the graphene/basalt fiber reinforced composite material comprises the following components in parts by weight: 2 to 5 parts of graphene, 2 to 5 parts of graphene dispersant, 15 to 20 parts of silanized basalt fiber, 50 to 65 parts of thermoplastic resin, 5 to 8 parts of modified filler, 8 to 10 parts of toughening agent, 3 to 5 parts of compatilizer and 0.1 to 1 part of flow modifier.
7. A method for preparing a graphene/basalt fiber reinforced composite material according to any one of claims 1 to 6, comprising:
at least uniformly mixing the graphene dispersoid and thermoplastic resin to obtain a mixture;
and adding the mixture into a main feeding port of an extruder in a forced feeding mode, and adding the silanized basalt fiber into a side feeding port of the extruder in a side feeding mode to obtain the graphene/basalt fiber reinforced composite material.
8. The method for preparing the graphene/basalt fiber reinforced composite material according to claim 7, wherein before at least the graphene dispersion and the thermoplastic resin are mixed uniformly to obtain a mixture, the method further comprises:
drying the thermoplastic resin; the drying temperature is 80-100 ℃, and the drying time is 4-6 hours; and/or the presence of a gas in the gas,
uniformly dispersing graphene and a graphene dispersing agent into water by using a planetary ball mill to obtain a graphene dispersion body.
9. The method for preparing the graphene/basalt fiber reinforced composite material according to claim 7, wherein the at least mixing the graphene dispersion and the thermoplastic resin to be uniform to obtain a mixture comprises:
stirring the graphene dispersoid, the thermoplastic resin, the modified filler, the toughening agent, the compatilizer and the flow modifier at the speed of 1000 r/min-1500 r/min for 1 minute-3 minutes, and then stirring at the speed of 500 r/min-1000 r/min for 1 minute-3 minutes to obtain a mixture.
10. The preparation method of the graphene/basalt fiber reinforced composite material according to claim 7, wherein the heating temperature of the extruder is 170 ℃ to 210 ℃, and the extrusion temperature of a machine head is 180 ℃ to 200 ℃;
the rotating speed of a main machine screw of the extruder is 200 r/min-300 r/min, and the feeding rotating speed is 20 r/min-30 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010506692.2A CN111518337A (en) | 2020-06-05 | 2020-06-05 | Graphene/basalt fiber reinforced composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010506692.2A CN111518337A (en) | 2020-06-05 | 2020-06-05 | Graphene/basalt fiber reinforced composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111518337A true CN111518337A (en) | 2020-08-11 |
Family
ID=71913133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010506692.2A Pending CN111518337A (en) | 2020-06-05 | 2020-06-05 | Graphene/basalt fiber reinforced composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111518337A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845735A (en) * | 2021-10-25 | 2021-12-28 | 武汉金发科技有限公司 | Thermal-aging-resistant polypropylene composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105086136A (en) * | 2015-07-30 | 2015-11-25 | 南京京锦元科技实业有限公司 | Preparation method of continuous basalt fiber reinforced flame-retardant PP master batch |
| CN105819710A (en) * | 2015-01-06 | 2016-08-03 | 中国科学院上海硅酸盐研究所 | Graphene/basalt composite material and production method thereof |
| CN106366434A (en) * | 2016-08-29 | 2017-02-01 | 广东石油化工学院 | Toughener-free compatibilizer-free basalt fiber reinforced polymer composition and preparation method thereof |
| CN106854343A (en) * | 2017-01-12 | 2017-06-16 | 四川航天五源复合材料有限公司 | Basalt fibre mixes reinforced resin and preparation method thereof, application with glass fibre |
| CN107815000A (en) * | 2017-10-31 | 2018-03-20 | 四川力智久创知识产权运营有限公司 | A kind of PE modified cable material of tension and preparation method thereof |
-
2020
- 2020-06-05 CN CN202010506692.2A patent/CN111518337A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819710A (en) * | 2015-01-06 | 2016-08-03 | 中国科学院上海硅酸盐研究所 | Graphene/basalt composite material and production method thereof |
| CN105086136A (en) * | 2015-07-30 | 2015-11-25 | 南京京锦元科技实业有限公司 | Preparation method of continuous basalt fiber reinforced flame-retardant PP master batch |
| CN106366434A (en) * | 2016-08-29 | 2017-02-01 | 广东石油化工学院 | Toughener-free compatibilizer-free basalt fiber reinforced polymer composition and preparation method thereof |
| CN106854343A (en) * | 2017-01-12 | 2017-06-16 | 四川航天五源复合材料有限公司 | Basalt fibre mixes reinforced resin and preparation method thereof, application with glass fibre |
| CN107815000A (en) * | 2017-10-31 | 2018-03-20 | 四川力智久创知识产权运营有限公司 | A kind of PE modified cable material of tension and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘朋等: "石墨烯均匀分散问题研究进展", 《材料导报》 * |
| 苏昱等: "玄武岩纤维增强聚丙烯复合材料性能研究", 《工程塑料应用》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845735A (en) * | 2021-10-25 | 2021-12-28 | 武汉金发科技有限公司 | Thermal-aging-resistant polypropylene composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585348B (en) | Toughened conducting material and preparation method for toughened conducting material | |
| CN106317934B (en) | A kind of degradable lightweight injection molding composite polyolefine material and preparation method thereof | |
| CN106220996B (en) | Silicon carbon black/composite polyolefine material preparation method | |
| CN103756125B (en) | A kind of PP composite material cross beams of automobile water tank and preparation method | |
| CN106589588A (en) | Flame-retardant enhanced-type polypropylene composite material and preparing method thereof | |
| CN111592667A (en) | Reinforced antibacterial artificial granite waste residue-based plastic master batch and preparation method thereof | |
| CN1962740A (en) | 6000 mesh inorganic powder filling-modified PE agglomerate and its preparation method | |
| CN102250419A (en) | Polypropylene composite material with improved interfacial compatibility and preparation method thereof | |
| CN102070831A (en) | Polypropylene-toughening compound material and preparation method thereof | |
| CN104387671A (en) | Preparation method of PA6 (polyamide 6)/PP (polypropylene)/carbon nano tube high-performance nano composite material | |
| CN101362849A (en) | Method for preparing polyester/nano calcium carbonate mixture | |
| CN104910539A (en) | High-impact while household electrical appliance ABS composite material and preparation method therefor | |
| CN104177696A (en) | Filling material master batch used for non-woven fabrics and preparing process thereof | |
| CN113929927A (en) | Polyvinyl alcohol-modified graphene oxide nano composite aqueous dispersion and preparation method thereof | |
| CN111518337A (en) | Graphene/basalt fiber reinforced composite material and preparation method thereof | |
| CN112266592B (en) | High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof | |
| CN1435437A (en) | Process for preparing graft polyolefin/lamellar silicate composite nanomaterial | |
| CN106633369A (en) | Preparation method of bi-component modified glass fiber filled composite polypropylene material | |
| CN101220127B (en) | Nucleocapsid type rubber coordination crosslinking agent | |
| CN111073040B (en) | Preparation method of HGM-CNTs bonding substance and light antistatic polypropylene material | |
| CN110643102A (en) | Bamboo fiber reinforced thermoplastic resin composite material and preparation method thereof | |
| CN105086162A (en) | Fibrilia-reinforced polypropylene engineering composite as well as preparation method and application of fibrilia-reinforced polypropylene engineering composite | |
| CN101585977B (en) | Preparation method of polypropylene reinforced plasticized modifier | |
| CN101735509A (en) | Micron-nano silicon carbide/polypropylene composite and preparation method thereof | |
| CN105733231A (en) | Calcium sulfate whisker-modified polycarbonate alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200811 |
|
| RJ01 | Rejection of invention patent application after publication |