CN107474531B - Glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material and preparation method thereof - Google Patents
Glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material and preparation method thereof Download PDFInfo
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- CN107474531B CN107474531B CN201710648520.7A CN201710648520A CN107474531B CN 107474531 B CN107474531 B CN 107474531B CN 201710648520 A CN201710648520 A CN 201710648520A CN 107474531 B CN107474531 B CN 107474531B
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- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 18
- 239000011521 glass Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000003365 glass fiber Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000007909 melt granulation Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 229920000515 polycarbonate Polymers 0.000 description 22
- 239000004417 polycarbonate Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010618 wire wrap Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material and a preparation method thereof, wherein the composite material is composed of a PA66-PC matrix, a modified graphene-carbon nanotube mixture, glass fibers, a silane coupling agent and epoxy resin. The injection product prepared by the composite material has good surface quality, internal layering phenomenon and excellent heat conduction and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a glass fiber-graphene-carbon nanotube mixed-filled PA66/PC composite material and a preparation method thereof.
Background
PA66 (polyamide 66 or nylon 66) has better impact resistance and higher strength, and is widely applied to manufacturing parts of mechanical, automobile, chemical and electrical devices, such as gears, rollers, pulleys, roller shafts, impellers in pump bodies, fan blades, high-pressure sealing rings, valve seats, gaskets, bushings, various handles, supporting frames, inner layers of wire wraps and the like. The PA66 has good wear resistance, heat resistance, oil resistance and chemical resistance, the water absorption rate and the shrinkage rate of raw materials are greatly reduced, the shrinkage rate of the PA66 is 1-2%, the shrinkage rate can be reduced to 0.2-1% by adding glass fiber, and the surface defects such as fiber floating, glass fiber leakage and the like are easily generated on the surface of a product after the glass fiber is added.
PA66 can be blended with other polymers (such as PC) to meet special requirements of different industries, and is widely used as a substitute for traditional materials such as metal, wood and the like. Polycarbonate (PC) has outstanding impact resistance and creep resistance, good cold resistance and heat resistance, low water absorption and stable product size. But also has the defects of poor processing fluidity, poor solvent resistance, easy stress cracking, sensitivity to notches and the like. The nylon (PA) has high mechanical strength and good melt fluidity and oil resistance, so that the PC and PA materials have good complementarity in performance. The PA66/PC composite material generally has the characteristics of good impact toughness, excellent chemical corrosion resistance and the like, and is an important synthetic material.
Disclosure of Invention
The invention aims to provide a glass fiber-graphene-carbon nanotube mixed and filled PA66/PC composite material, which is prepared from raw materials including a matrix composed of PA66 and PC, a modified graphene mixture, glass fibers, a silane coupling agent and epoxy resin, wherein the weight ratio of the matrix to the glass fibers to the modified graphene mixture is 7:3:0.6-1.2, and the use amounts of the silane coupling agent and the epoxy resin are 0.1-0.2% and 0.2% of the weight of the composite material respectively, wherein the modified graphene mixture is prepared by uniformly mixing graphene and carbon nanotubes according to the mass ratio of 1-5:1, adding the mixture into a concentrated sulfuric acid solution with the mass fraction of 82-86%, stirring at normal temperature for 7-14min, filtering, neutralizing, washing, redispersing an ethanol solution, standing, and freeze-drying.
In the scheme, the weight ratio of the PA66 to the PC in the matrix is 1: 0.5-1.5.
In the above scheme, the silane coupling agent is Si 550.
The invention also aims to provide a preparation method of the glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material, which specifically comprises the following steps: (1) uniformly mixing graphene and carbon nanotubes in proportion, adding the graphene mixture into a concentrated sulfuric acid solution, stirring at normal temperature for 7-14min, adding water to dilute, filtering, washing filter residues with an alkali solution for multiple times, washing with water to be neutral, dispersing the filter residues in an ethanol solution, adding glass fibers, stirring, refrigerating at 0-4 ℃ for 12-18h, and freeze-drying to obtain a modified graphene-glass fiber mixture; (2) and uniformly mixing the modified graphene-glass fiber mixture, the PA66/PC matrix, the silane coupling agent and the epoxy resin, and performing melt granulation by a double-screw extruder to obtain the modified graphene-glass fiber composite material.
In the scheme, graphene and carbon nano tubes are mixed according to the mass ratio of 1-5:1, the mass fraction of concentrated sulfuric acid is 82-86%, the alkali solution is 0.1-0.3mol/L NaOH solution, and the volume fraction of the ethanol solution is 40-60%.
In the scheme, the weight ratio of the PA66/PC matrix to the glass fiber to the modified graphene mixture is 7:3:0.6-1.2, and the use amounts of the silane coupling agent and the epoxy resin are respectively 0.1-0.2% and 0.2% of the weight of the composite material.
In the scheme, the length-diameter ratio of a double-screw extruder used for extrusion granulation is 1:30-40, the rotating speed is 330rad/s, and the melting temperature is 240-.
Compared with the prior art, the invention has the following beneficial effects: (1) the glass fiber and the modified graphene are mixed in advance and are uniformly dispersed in advance by using ethanol, so that the glass fiber and the modified graphene can be conveniently dispersed in a PA66/PC matrix, and the surface quality of an injection molding product can be improved; (2) the silane coupling agent and the epoxy resin in the formula are beneficial to compounding the filler and the matrix, so that the phenomenon of layering is avoided, and the mechanical property of the composite material is improved; (3) the addition of the graphene can endow the composite material with better heat conduction and mechanical properties.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
The raw materials used in the invention are all sold in the common market.
Example 1
The glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material is prepared from the following raw materials in parts by weight: PA 6635 parts, PC35 parts, modified graphene mixture 6 parts (the mass ratio of graphene to carbon nano tube is 5:1), glass fiber 30 parts, silane coupling agent Si5500.15 parts and epoxy resin about 0.2 part.
Firstly, uniformly mixing weighed graphene and carbon nano tubes according to a proportion, then adding the mixture into a concentrated sulfuric acid solution with the mass fraction of 82%, stirring at normal temperature for 7-14min, adding water for dilution, filtering, washing filter residues for multiple times by using a 0.1-0.3mol/L NaOH solution, then washing with water to be neutral, dispersing the filter residues in an ethanol solution with the volume fraction of 60%, then adding glass fibers, stirring, then placing in an environment with the temperature of 0-4 ℃, refrigerating for 12-18h, and freeze-drying to obtain the modified graphene-glass fiber mixture.
And then uniformly mixing the modified graphene-glass fiber mixture, the PA66/PC matrix, the silane coupling agent and the epoxy resin, and performing melt granulation by a double-screw extruder to obtain the graphene/PC/PA/PC/PA. The technological parameters are as follows: the length-diameter ratio of the double-screw extruder is 1:30-40, the rotating speed is 330rad/s, and the melting temperature is 240-.
Example 2
The glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material is prepared from the following raw materials in parts by weight: PA 6640 parts, PC30 parts, modified graphene mixture 10 parts (the mass ratio of graphene to carbon nano tube is 3:1), glass fiber 30 parts, silane coupling agent Si5500.11 parts and epoxy resin about 0.22 part.
Firstly, uniformly mixing weighed graphene and carbon nano tubes according to a proportion, then adding the mixture into a concentrated sulfuric acid solution with the mass fraction of 85%, stirring at normal temperature for 7-14min, adding water for dilution, filtering, washing filter residues for multiple times by using a 0.1-0.3mol/L NaOH solution, then washing the filter residues to be neutral by using water, dispersing the filter residues in an ethanol solution with the volume fraction of 40%, then adding glass fibers, stirring, then placing in an environment with the temperature of 0-4 ℃, refrigerating for 12-18h, and freeze-drying to obtain the modified graphene-glass fiber mixture.
And then uniformly mixing the modified graphene-glass fiber mixture, the PA66/PC matrix, the silane coupling agent and the epoxy resin, and performing melt granulation by a double-screw extruder to obtain the graphene/PC/PA/PC/PA. The technological parameters are as follows: the length-diameter ratio of the double-screw extruder is 1:30-40, the rotating speed is 330rad/s, and the melting temperature is 240-.
The plastic part formed by injection molding of the PA66/PC composite material prepared by the invention has the advantages that no fiber floating and glass fiber leakage phenomena exist on the surface of the product immediately under high filling, the tensile strength and the heat resistance are improved to a certain degree, no layering phenomenon is found through further microscopic observation, and the product is good in public praise of customers.
Claims (1)
1. The glass fiber-graphene-carbon nanotube mixed and filled PA66/PC composite material is characterized in that raw materials of the composite material comprise a matrix consisting of PA66 and PC, a modified graphene mixture, glass fibers, a silane coupling agent and epoxy resin, wherein the weight ratio of the matrix to the glass fibers to the modified graphene mixture is 7:3:0.6-1.2, and the use amounts of the silane coupling agent and the epoxy resin are respectively 0.1-0.2% and 0.2% of the weight of the composite material; the weight ratio of PA66 to PC in the matrix is 1:0.5-1.5, and the silane coupling agent is Si 550; the preparation method of the composite material comprises the following steps: (1) mixing graphene and carbon nanotubes according to a mass ratio of 1-5:1, adding the obtained mixture into a concentrated sulfuric acid solution with a mass fraction of 82-86%, stirring at normal temperature for 7-14min, adding water for dilution, filtering, washing filter residues with 0.1-0.3mol/L NaOH solution for multiple times, and washing with water until the filter residues are neutral, wherein the obtained filter residues are the modified graphene mixture; dispersing the modified graphene mixture in 40-60% ethanol solution by volume, adding glass fiber, stirring, refrigerating at 0-4 ℃ for 12-18h, and freeze-drying to obtain a modified graphene-glass fiber mixture; (2) uniformly mixing the modified graphene-glass fiber mixture, a PA66/PC matrix, a silane coupling agent and epoxy resin, and performing melt granulation by using a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 1:30-40, the rotating speed is 330rad/s, and the melting temperature is 240-.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710648520.7A CN107474531B (en) | 2017-08-01 | 2017-08-01 | Glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material and preparation method thereof |
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|---|---|---|---|
| CN201710648520.7A CN107474531B (en) | 2017-08-01 | 2017-08-01 | Glass fiber-graphene-carbon nanotube mixed filled PA66/PC composite material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107474531B true CN107474531B (en) | 2020-11-10 |
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| CN108117743B (en) * | 2018-01-19 | 2021-02-12 | 广州润锋科技股份有限公司 | Carbon nanotube modified high-conductivity nylon composite material and preparation method thereof |
| CN108948468B (en) * | 2018-08-01 | 2021-02-05 | 安徽锦华氧化锌有限公司 | Preparation method of graphene oxide-glass fiber-alumina filling modified oil-resistant corrosion-resistant vulcanized rubber compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443204A (en) * | 2011-01-18 | 2013-12-11 | 巴斯夫欧洲公司 | thermoplastic molding composition |
| CN104292817A (en) * | 2014-01-08 | 2015-01-21 | 上海智高贸易有限公司 | Continuous fiber composite high thermal conductive material and processing technology thereof |
| CN106832905A (en) * | 2017-02-28 | 2017-06-13 | 四川大学 | Polymer matrix micro-/ nano composite material powder and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443204A (en) * | 2011-01-18 | 2013-12-11 | 巴斯夫欧洲公司 | thermoplastic molding composition |
| CN104292817A (en) * | 2014-01-08 | 2015-01-21 | 上海智高贸易有限公司 | Continuous fiber composite high thermal conductive material and processing technology thereof |
| CN106832905A (en) * | 2017-02-28 | 2017-06-13 | 四川大学 | Polymer matrix micro-/ nano composite material powder and preparation method thereof |
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