CN117511191A - Glass fiber reinforced nylon composite material based on amorphous nylon composite and preparation method thereof - Google Patents
Glass fiber reinforced nylon composite material based on amorphous nylon composite and preparation method thereof Download PDFInfo
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- CN117511191A CN117511191A CN202311429852.8A CN202311429852A CN117511191A CN 117511191 A CN117511191 A CN 117511191A CN 202311429852 A CN202311429852 A CN 202311429852A CN 117511191 A CN117511191 A CN 117511191A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 93
- 229920001778 nylon Polymers 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 239000003365 glass fiber Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004982 aromatic amines Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 17
- 238000007667 floating Methods 0.000 abstract description 16
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical group CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance 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
- 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
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a glass fiber reinforced nylon composite material based on amorphous nylon composite and a preparation method thereof, wherein the glass fiber reinforced nylon composite material comprises the following components in parts by weight: 40-70 parts of high-temperature nylon, 5-20 parts of amorphous nylon and Ti 3 AlC 2 5-10 parts of composite PPO material, 10-50 parts of glass fiber and 0.1-1 part of antioxidant. The invention effectively reduces the crystallinity of high-temperature nylon and improves the compatibility of resin and glass fiber by adding amorphous nylon (the main component is PA 6I/6T), thereby not only solving the fiber floating problem on the surface of a finished piece, but also greatly improving the warping problem of a thin-wall finished pieceThe problem is that the dimensional stability of the thin-walled workpiece is greatly improved. Meanwhile, the composite material still has excellent mechanical property, heat resistance and wear resistance.
Description
Technical Field
The invention relates to a glass fiber reinforced nylon composite material based on amorphous nylon composite and a preparation method thereof, belonging to the technical field of composite materials.
Background
The high temperature resistant nylon PPA is nylon engineering plastics which can be used for a long time at 150 ℃. The high temperature resistant nylon PPA has good performances in heat, electricity, physical and chemical resistance, has high rigidity and strength at high temperature and excellent dimensional accuracy and stability, and is widely applied to the fields of electronic appliances, automobile industry and the like. In order to obtain better mechanical and heat resistance, the high-temperature nylon is generally reinforced and modified by adding a certain amount of glass fibers, and the glass fiber reinforced and modified high-temperature nylon has excellent mechanical and heat resistance, but because the crystallinity of the high-temperature nylon and the orientation of the glass fibers in the injection molding direction cause the difference of shrinkage of the material in the transverse and longitudinal directions, the warping problem of the thin-wall workpiece is caused. Meanwhile, the binding force between the glass fiber and the high-temperature nylon resin matrix is not strong enough, so that the surface of the injection molding part has the problem of floating fiber, and the appearance of the part is affected.
Disclosure of Invention
The invention aims to provide a glass fiber reinforced nylon composite material based on amorphous nylon composite and a preparation method thereof, wherein by adding amorphous nylon (the main component is PA 6I/6T), the crystallization of high-temperature nylon is effectively reduced, the compatibility of resin and glass fiber is improved, the fiber floating problem on the surface of a workpiece is solved, the warping problem of a thin-wall workpiece is also greatly improved, and the dimensional stability of the thin-wall workpiece is greatly improved. Meanwhile, the composite material still has excellent mechanical property, heat resistance and wear resistance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the glass fiber reinforced nylon composite material based on amorphous nylon composite comprises the following components in parts by weight: 40-70 parts of high-temperature nylon, 5-20 parts of amorphous nylon and Ti 3 AlC 2 5-10 parts of composite PPO material, 10-50 parts of glass fiber and 0.1-1 part of antioxidant.
Preferably, said Ti 3 AlC 2 The preparation method of the composite PPO material comprises the following steps: ti is mixed with 3 AlC 2 For granulesFunctionalization of the silane coupling agent; to be functionalized with Ti 3 AlC 2 Placing the particles and PPO in DMF respectively, mixing, adding BPO to initiate reaction, stirring to obtain a mixed system, solidifying the mixed system, and pulverizing to obtain Ti 3 AlC 2 Composite PPO material.
Preferably, said Ti 3 AlC 2 The specific method for functionalizing the particles by using the silane coupling agent is as follows: ti is mixed with 3 AlC 2 Dispersing the particles in a solvent, and adjusting the pH to 3-4; then dripping the silane coupling agent into the system, heating and stirring to obtain a mixed solution; cooling the mixed solution, centrifuging, drying, grinding and sieving to obtain functionalized Ti 3 AlC 2 And (3) particles.
Preferably, said Ti 3 AlC 2 Dispersing the particles in a solvent through ultrasonic treatment, wherein the ultrasonic frequency is 30-60KHz, and the treatment time is 1-2h; the pH was adjusted by glacial acetic acid.
Preferably, the silane coupling agent is MTEs, and the dosage is Ti 3 AlC 2 3-5% of the mass of the particles, heating to 45-60 ℃, stirring for 4-6h, and stirring at 200-500rpm; centrifuging at 4500-6000rpm for 10-20min; drying and treating at 90-120deg.C for 20-24 hr.
Preferably, said Ti 3 AlC 2 The mass ratio of the catalyst to PPO is (3-6) (14-17); the adding amount of BPO is 1-3% of the mass of PPO.
Preferably, the initiation reaction is carried out at 30-50 ℃, ultrasonic stirring is carried out for 1-2h, ultrasonic frequency is 30-60KHz, and stirring speed is 300-500rpm.
Preferably, the mixed system is dried at 85-100 ℃ for 1.5-3 hours and then cured at 130-160 ℃ for 2-3 hours.
Preferably, the high-temperature nylon has a melting point of 300-320 ℃; the glass fiber is a chopped glass fiber with the surface coated with a silane-based impregnating compound, and the water content is less than or equal to 0.1%; the antioxidant is aromatic amine antioxidant.
The preparation method of any glass fiber reinforced nylon composite material based on amorphous nylon composite comprises the steps of weighing all components according to a proportion, uniformly mixing, and extruding and granulating; the extrusion granulation is carried out by an extruder, the rotating speed of the extruder is 200-400rpm, and the extrusion temperature is 280-330 ℃.
The invention has the beneficial effects that:
1. the amorphous nylon (PA 6I/6T) material has high fluidity and non-crystallinity, the cooling speed is slower than that of high-temperature nylon during injection molding, when molten plastic contacts a mold, the high-temperature nylon has an inward cooling shrinkage acting force, and the inward shrinkage force of the amorphous nylon is relatively much smaller, so that the amorphous nylon is coated on the surface of the material, and the surface of a workpiece is free from floating fiber and is smooth. The amorphous nylon has high fluidity and amorphous property, so that on one hand, the crystallinity of the high-temperature nylon can be reduced, and on the other hand, the compatibility between the resin matrix and the glass fiber can be enhanced, and the warping problem of the thin-wall part caused by the orientation of the glass fiber and the crystallization of the high-temperature nylon during injection molding can be reduced.
2、Ti 3 AlC 2 After the particles are functionalized by the silane coupling agent, the particles can form a functional bridging effect with PPO polymer molecules, so that the effective bonding and interface interaction between inorganic particles and polymer molecules are enhanced, and Ti is caused 3 AlC 2 The particles can be better dispersed in the composite material, and Ti can be avoided 3 AlC 2 Agglomeration of particles; and at Ti 3 AlC 2 After the composite PPO material and the rest components are melted, blended and granulated, ti 3 AlC 2 The particles can be better dispersed in the high-temperature nylon composite material and are not easy to fall off, and the mechanical property, heat resistance and wear resistance of the composite material can be further improved.
Detailed Description
The present invention will be specifically described with reference to examples.
The high temperature nylon used in the following examples or comparative examples is a semi-aromatic high temperature nylon having a melting point between 300 ℃ and 320 ℃. Amorphous nylon (PA 6I/6T) is a semi-aromatic amorphous nylon having excellent barrier properties against various solvents such as aromatic, hydrocarbon, strong sodium oxide solution, ethanol, water, etc. The glass fiber is chopped glass fiber, and the surface of the chopped glass fiber is coated with silane-based impregnating compound, so that the glass fiber has the characteristics of small static electricity, good fluidity and high temperature resistance. The chopped glass fibers were 3mm in length and 10mm in diameter. The moisture content of the chopped glass fibers was less than 0.1% (ISO 3344). The antioxidant is an aromatic amine antioxidant with no color change, and is especially suitable for resisting thermal oxidation aging at high temperature.
Methyl methacrylate-terminated low molecular weight PPO resins were purchased from dongguan, macros plastics materials limited. N, N-Dimethylformamide (DMF) and Benzoyl Peroxide (BPO) were purchased from Metropolis Kelong chemical reagent plant. Methyltriethoxysilane (MTEs) is purchased from Qiao Xuanhua company, guangzhou.
Example 1
The components and the amounts used are as follows:
| component (A) | Dosage (wt%) |
| High temperature nylon | 59.7 |
| Amorphous nylon | 5 |
| Ti 3 AlC 2 Composite PPO material | 5 |
| Glass fiber | 30 |
| Antioxidant | 0.3 |
Wherein Ti is 3 AlC 2 Composite PPO materialThe preparation method of the material comprises the following steps: ti is mixed with 3 AlC 2 Dispersing the particles in absolute ethyl alcohol/deionized water (volume ratio is 8/1), performing ultrasonic treatment (50 KHz) for 1h, then dripping glacial acetic acid into the system, and regulating the pH of the system to 3-4. MTEs (mass is Ti) 3 AlC 2 5% of the mass of the particles) was added dropwise to the system, heated to 50℃and stirred at 4500rpm for 4h to allow the coupling agent to adsorb to Ti 3 AlC 2 The surface of the particles. The mixed solution was then cooled to room temperature and centrifuged at 5000rpm for 15min using a high speed centrifuge. And drying the centrifuged precipitate in a vacuum drying oven at 100 ℃ for 24 hours to volatilize the solvent. Grinding and sieving the precipitate to obtain Ti with MTES function 3 AlC 2 And (3) particles.
To be functionalized with Ti 3 AlC 2 Adding the particles into DMF, and carrying out ultrasonic treatment to obtain a suspension; PPO is dissolved in DMF to obtain a transparent solution, wherein Ti 3 AlC 2 The mass ratio of the particles to the PPO is 3:17; the two solutions were mixed, and then BPO (mass: 2% of PPO mass) was added at 35℃to initiate the reaction, and the mixture was sonicated (50 KHz) and stirred (400 rpm) for 1 hour to obtain a mixed system. Transferring the mixed system into a mold, placing in an oven at 90deg.C for 2 hr to volatilize solvent and discharge air bubbles, solidifying at 150deg.C for 2, cooling to room temperature, and pulverizing to obtain Ti 3 AlC 2 Composite PPO material.
The preparation method of the high-temperature nylon composite material comprises the following steps: high temperature nylon, amorphous nylon and Ti 3 AlC 2 The composite PPO material and the antioxidant are respectively weighed according to the proportion, added into a high-speed mixer, evenly mixed, added from a main feeding port of an extruder through a weightless scale, added from the side of the extruder through the weightless scale, extruded and granulated at the processing temperature of 300 ℃ at the rotating speed of 400 rpm.
Example 2
The components and the amounts used are as follows:
| component (A) | Dosage (wt%) |
| High temperature nylon | 54.7 |
| Amorphous nylon | 10 |
| Ti 3 AlC 2 Composite PPO material | 5 |
| Glass fiber | 30 |
| Antioxidant | 0.3 |
Wherein Ti is 3 AlC 2 The preparation method of the composite PPO material and the preparation method of the high-temperature nylon composite material are the same as in example 1.
Comparative example 1
The components and the amounts used are as follows:
| component (A) | Dosage (wt%) |
| High temperature nylon | 64.7 |
| Ti 3 AlC 2 Composite PPO material | 5 |
| Glass fiber | 30 |
| Antioxidant | 0.3 |
Wherein Ti is 3 AlC 2 The preparation method of the composite PPO material comprises the following steps: ti is mixed with 3 AlC 2 Dispersing the particles in absolute ethyl alcohol/deionized water (volume ratio is 8/1), performing ultrasonic treatment (50 KHz) for 1h, then dripping glacial acetic acid into the system, and regulating the pH of the system to 3-4. MTEs (mass is Ti) 3 AlC 2 5% of the mass of the particles) was added dropwise to the system, heated to 50℃and stirred at 4500rpm for 4h to allow the coupling agent to adsorb to Ti 3 AlC 2 The surface of the particles. The mixed solution was then cooled to room temperature and centrifuged at 5000rpm for 15min using a high speed centrifuge. And drying the centrifuged precipitate in a vacuum drying oven at 100 ℃ for 24 hours to volatilize the solvent. Grinding and sieving the precipitate to obtain Ti with MTES function 3 AlC 2 And (3) particles.
To be functionalized with Ti 3 AlC 2 Adding the particles into DMF, and carrying out ultrasonic treatment to obtain a suspension; PPO is dissolved in DMF to obtain a transparent solution, wherein Ti 3 AlC 2 The mass ratio of the particles to the PPO is 3:17; the two solutions were mixed, and then BPO (mass: 2% of PPO mass) was added at 35℃to initiate the reaction, and the mixture was sonicated (50 KHz) and stirred (400 rpm) for 1 hour to obtain a mixed system. Transferring the mixed system into a mold, placing in an oven at 90deg.C for 2 hr to volatilize solvent and discharge air bubbles, solidifying at 150deg.C for 2, cooling to room temperature, and pulverizing to obtain Ti 3 AlC 2 Composite PPO material.
The preparation method of the high-temperature nylon composite material comprises the following steps: nylon, ti at high temperature 3 AlC 2 The composite PPO material and the antioxidant are respectively weighed according to the proportion and added with high contentAfter being mixed uniformly in a mixer, the glass fiber is fed from the main feeding port of an extruder through a weightless scale, and the glass fiber is extruded and granulated at the processing temperature of 300 ℃ at the rotating speed of 400 rpm.
Comparative example 2
The components and the amounts used are as follows:
| component (A) | Dosage (wt%) |
| High temperature nylon | 64.7 |
| Amorphous nylon | 5 |
| Glass fiber | 30 |
| Antioxidant | 0.3 |
The preparation method of the high-temperature nylon composite material comprises the following steps: the high-temperature nylon, the amorphous nylon and the antioxidant are respectively weighed according to the proportion, added into a high-speed mixer, added from a main feeding port of an extruder through a weightless scale, added from the side of the extruder through the weightless scale, extruded and granulated at the processing temperature of 300 ℃ at the rotating speed of 400 rpm.
Comparative example 3
Substantially the same as in example 1, except that Ti 3 AlC 2 The particles were not functionalized.
The components and the amounts used are as follows:
wherein Ti is 3 AlC 2 The preparation method of the composite PPO material comprises the following steps: ti is mixed with 3 AlC 2 Adding the particles into DMF, and carrying out ultrasonic treatment to obtain a suspension; PPO is dissolved in DMF to obtain a transparent solution, wherein Ti 3 AlC 2 The mass ratio of the particles to the PPO is 3:17; the two solutions were mixed, and then BPO (mass: 2% of PPO mass) was added at 35℃to initiate the reaction, and the mixture was sonicated (50 KHz) and stirred (400 rpm) for 1 hour to obtain a mixed system. Transferring the mixed system into a mold, placing in an oven at 90deg.C for 2 hr to volatilize solvent and discharge air bubbles, solidifying at 150deg.C for 2, cooling to room temperature, and pulverizing to obtain Ti 3 AlC 2 Composite PPO material.
The preparation method of the high-temperature nylon composite material comprises the following steps: high temperature nylon, amorphous nylon and Ti 3 AlC 2 The composite PPO material and the antioxidant are respectively weighed according to the proportion, added into a high-speed mixer, evenly mixed, added from a main feeding port of an extruder through a weightless scale, added from the side of the extruder through the weightless scale, extruded and granulated at the processing temperature of 300 ℃ at the rotating speed of 400 rpm.
The prepared plastic particles are dried for 4 hours at 120 ℃ and then are injection molded into standard sample bars for testing, and the method for testing the related performance is as follows:
tensile strength: the test conditions were 23℃and 10mm/min, determined according to ISO 527-2.
Flexural strength: the test conditions were 23℃and 2mm/min, determined according to ISO 178.
Flexural modulus: the test conditions were 23℃and 2mm/min, determined according to ISO 178.
Cantilever beam notch impact: the test conditions were 23℃as determined according to ISO 180.
And (3) warping: samples were injection molded into 100mm x 1mm square plates and after standing overnight at 23 ℃, the warpage was classified into three classes according to the difference in height (Δh) between the warpage of the square plate and the horizontal plane as viewed in horizontal position: slight warpage (0 < [ delta ] h < 1 mm), apparent warpage (1 mm < [ delta ] h < 3 mm), severe warpage (3 mm < [ delta ] h < 10 mm).
Heat distortion temperature: the test conditions were 1.8MPa, determined according to ISO 75.
Surface fiber floating condition: samples were injection molded into 100mm x 1mm square boards, and were classified into three classes according to the float fiber condition: no floating fiber, slight floating fiber and obvious floating fiber.
Abrasion loss test: adopting GB/T5478 plastic rolling abrasion test, H22 grinding wheel (ceramic); load 0.5KG; the rotation speed is 60rpm; sample thickness 3mm, test 25000 samples abrasion after rotation;
the test results were as follows:
| example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile strength, MPa | 215 | 220 | 175 | 180 | 203 |
| Flexural Strength, MPa | 330 | 340 | 270 | 280 | 320 |
| Flexural modulus, MPa | 14600 | 15000 | 12000 | 13400 | 14000 |
| Notched impact of cantilever beam, KJ/m 2 | 23 | 24 | 16 | 18 | 20 |
| Heat distortion temperature, DEG C | 285 | 285 | 280 | 280 | 285 |
| Warp, Δh, mm | 0.5 | 0.4 | 4.2 | 2.8 | 0.5 |
| Warp rating | Slightly warp | Slightly warp | Severe warpage | Obvious warp | Slightly warp |
| Surface fiber floating condition | No floating fiber | No floating fiber | Obvious floating fiber | Slightly floating fiber | No floating fiber |
| Wear-resistant g | 0.157 | 0.152 | 0.278 | 0.326 | 0.246 |
As can be seen from the test data of examples 1-2 and comparative examples 1-3, after amorphous nylon (PA 6I/6T) is added, the mechanical properties of the material are kept good, the warping and surface floating fiber are obviously improved, and the heat resistance of the material is not reduced. With the increase of the content of the amorphous nylon (PA 6I/6T), the impact performance of the material is improved to a certain extent, which indicates that the amorphous nylon (PA 6I/6T) improves the compatibility of the glass fiber and the resin matrix. In combination, the amorphous nylon (PA 6I/6T) used in the invention has good comprehensive effect, and the addition of the amorphous nylon (PA 6I/6T) can effectively promote the compatibility of glass fiber and a resin matrix, thereby improving the mechanical property of the material. Meanwhile, amorphous nylon (PA 6I/6T) can migrate to the surface of a material due to high fluidity, so that the surface fiber floating condition of an injection molding product is greatly improved, and the problem of warping of a thin-wall product caused by glass fiber orientation and high-temperature nylon crystallization during injection molding is reduced.
Meanwhile, it can be further seen from the test data of examples 1-2 and comparative example 3 that Ti 3 AlC 2 The particles are added into the system through the functionalization of the silane coupling agent, so that the mechanical property and the wear resistance of the material can be improved, and the heat resistance of the material is not reduced; the reason for this is that the functionalized Ti 3 AlC 2 The particles can form functional bridging action with PPO polymer molecules, so that the effective bonding and interfacial interaction between inorganic particles and polymer molecules are enhanced, and Ti is caused 3 AlC 2 The particles can be better dispersed in the composite material, and Ti can be avoided 3 AlC 2 Agglomeration of particles; at Ti 3 AlC 2 After the composite PPO material and the rest components are melted, blended and granulated, ti 3 AlC 2 The particles are used as wear-resistant materials, can be better dispersed in the high-temperature nylon composite material and are not easy to fall off, and then the mechanical property, the heat resistance and the wear resistance of the composite material can be improved.
The foregoing is merely illustrative of the preferred embodiments of this invention, and it will be appreciated by those skilled in the art that variations and modifications may be made without departing from the principles of this invention, and such variations and modifications are to be regarded as being within the scope of this invention.
Claims (9)
1. The glass fiber reinforced nylon composite material based on amorphous nylon composite is characterized by comprising the following components in parts by weight: 40-70 parts of high-temperature nylon, 5-20 parts of amorphous nylon and Ti 3 AlC 2 5-10 parts of composite PPO material, 10-50 parts of glass fiber and 0.1-1 part of antioxidant;
Ti 3 AlC 2 the preparation method of the composite PPO material comprises the following steps: ti is mixed with 3 AlC 2 The particles are functionalized with a silane coupling agent; to be functionalized with Ti 3 AlC 2 Placing the particles and PPO in DMF respectively, mixing, adding BPO to initiate reaction, stirring to obtain a mixed system, solidifying the mixed systemPulverizing to obtain Ti 3 AlC 2 Composite PPO material.
2. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the Ti is 3 AlC 2 The specific method for functionalizing the particles by using the silane coupling agent is as follows: ti is mixed with 3 AlC 2 Dispersing the particles in a solvent, and adjusting the pH to 3-4; then dripping the silane coupling agent into the system, heating and stirring to obtain a mixed solution; cooling the mixed solution, centrifuging, drying, grinding and sieving to obtain functionalized Ti 3 AlC 2 And (3) particles.
3. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the Ti is 3 AlC 2 Dispersing the particles in a solvent through ultrasonic treatment, wherein the ultrasonic frequency is 30-60KHz, and the treatment time is 1-2h; the pH was adjusted by glacial acetic acid.
4. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the silane coupling agent is MTEs, and the dosage is Ti 3 AlC 2 3-5% of the mass of the particles, heating to 45-60 ℃, stirring for 4-6h, and stirring at 200-500rpm; centrifuging at 4500-6000rpm for 10-20min; drying and treating at 90-120deg.C for 20-24 hr.
5. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the Ti is 3 AlC 2 The mass ratio of the catalyst to PPO is (3-6) (14-17); the adding amount of BPO is 1-3% of the mass of PPO.
6. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the initiation reaction is carried out at 30-50 ℃, ultrasonic stirring is carried out for 1-2 hours, ultrasonic frequency is 30-60KHz, and stirring speed is 300-500rpm.
7. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the mixed system is cured at 130-160 ℃ for 2-3 hours after being dried at 85-100 ℃ for 1.5-3 hours.
8. The glass fiber reinforced nylon composite material based on amorphous nylon composite according to claim 1, wherein the high-temperature nylon has a melting point of 300-320 ℃; the glass fiber is a chopped glass fiber with the surface coated with a silane-based impregnating compound, and the water content is less than or equal to 0.1%; the antioxidant is aromatic amine antioxidant.
9. The preparation method of the glass fiber reinforced nylon composite material based on amorphous nylon composite according to any one of claims 1 to 8, which is characterized in that the glass fiber reinforced nylon composite material is prepared by weighing the components according to the proportion, uniformly mixing, and extruding and granulating; the extrusion granulation is carried out by an extruder, the rotating speed of the extruder is 200-400rpm, and the extrusion temperature is 280-330 ℃.
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