CN105295363A - Alcoholysis-tolerant nylon composite for automobile and processing method for alcoholysis-tolerant nylon composite - Google Patents
Alcoholysis-tolerant nylon composite for automobile and processing method for alcoholysis-tolerant nylon composite Download PDFInfo
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- CN105295363A CN105295363A CN201510851444.0A CN201510851444A CN105295363A CN 105295363 A CN105295363 A CN 105295363A CN 201510851444 A CN201510851444 A CN 201510851444A CN 105295363 A CN105295363 A CN 105295363A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 77
- 229920001778 nylon Polymers 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000003672 processing method Methods 0.000 title abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 132
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 37
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 35
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 30
- 239000002667 nucleating agent Substances 0.000 claims abstract description 30
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 27
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000000155 melt Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 5
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- -1 calcium carboxylate Chemical class 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 238000005520 cutting process Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
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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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- 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
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses an alcoholysis-tolerant nylon composite for an automobile. The alcoholysis-tolerant nylon composite consists of the following components in percentage by weight: 58-63% of nylon resin, 35-40% of pretreated glass fibers, 0.1-0.5% of a nucleating agent, 0.3-0.5% of an antioxidant, 0.5-0.7% of a lubricant and 0.3-0.5% of a heat stabilizer; ultrasonic waves and mechanical vibration are adopted for front and back combination, and a silane coupling agent and a PPE melt are utilized for conducting impregnation pretreatment on the glass fiber. The invention further discloses a processing method for the alcoholysis-tolerant nylon composite for the automobile. No alcoholysis-tolerant agent needs to be added in the nylon composite, and the alcoholysis-tolerant performance can be improved when the physical property of the nylon composite is not reduced; the nylon composite has excellent alcoholysis-tolerant performance, and can meet the TL-VW774 testing requirements, the sample surface is good and has no changes and cracks; not only is the problem in the prior art that the alcoholysis-tolerant performance can be met by adding the alcoholysis-tolerant agent or an alcoholysis-resistant agent solved, but also the problem in the prior art that the mechanical property of a base material is obviously reduced after adding PPE is solved.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to an alcoholysis-resistant nylon composite material for automobiles and a processing method thereof.
Background
With the rapid development of the automobile industry, plastics are becoming the trend and direction of the development of automobile materials instead of steel, and glass fiber reinforced nylon materials are widely applied to water chamber parts of automobiles, such as thermostat housings, water tank connectors and the like, due to the excellent heat resistance, mechanical properties and the like of the materials. The parts not only require the material to have excellent mechanical properties, but also require the material to have good hydrolysis resistance and alcoholysis resistance, and can be used in a mixed solution of hot water and antifreeze solution ethylene glycol for a long time without reducing the performance.
Materials used for automobile water chamber components are required to be resistant to glycol solution and other chemical corrosive agents and corrosion of aqueous solution with the temperature of more than 100 ℃, meanwhile, stress cracking is not allowed to occur at joints in the assembling process, and the common nylon materials are difficult to meet the requirements.
In the prior art, most alcoholysis-resistant materials achieve alcoholysis resistance by adding an alcoholysis-resistant agent or an alcoholysis-resistant agent, and although the alcoholysis-resistant property of the materials is improved, the overall performance of the materials is reduced; meanwhile, due to the higher processing temperature, the alcoholysis resistant agent or the alcoholysis resistant agent can be decomposed, so that the capability of resisting the corrosion of the frozen liquid of the whole material is reduced, and the production quality and the production efficiency are influenced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a nylon composite material with excellent long-term alcoholysis resistance, and solves the problem that in the prior art, an alcoholysis resistance agent or an alcoholysis resistance agent needs to be added to meet the alcoholysis resistance requirement; the nylon composite material does not need to be added with an alcoholysis resistant agent, not only maintains the original physical properties, but also has alcoholysis resistant chemical properties meeting the technical requirements of TL-VW774, namely: the product has good and unchanged surface and no crack after being placed in 100 percent glycol solution for 48 hours at the constant temperature of 135 ℃, and has excellent mechanical property. The invention also provides a processing method of the alcoholysis-resistant nylon composite material for the automobile.
The invention adopts the following technical scheme:
the alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight:
58 to 63 percent of nylon resin
35-40% of pretreated glass fiber
0.1 to 0.5 percent of nucleating agent
0.3 to 0.5 percent of antioxidant
0.5 to 0.7 percent of lubricant
0.3-0.5% of a heat stabilizer; wherein,
the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent = (30-40): (5-10): (0.5-1), wherein the silane coupling agent is any one selected from 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane and diethylenetriaminopropyltrimethoxysilane;
b. immersing common continuous glass fibers into the mixed solution, carrying out ultrasonic treatment for 15-20 min at the frequency of 70-80 KHz, and standing for 50-60 min; then, mechanically vibrating for 40-60 min at 500-600 Hz and 0.5-1.5 mm in amplitude; taking out the glass fiber, washing the glass fiber with acetone for 2 times, and drying the glass fiber at the temperature of 100-150 ℃ for 60-90 min;
c. b, immersing the glass fiber dried in the step b into the mixed solution, performing ultrasonic treatment for 25-30 min at the frequency of 40-50 KHz, and standing for 50-60 min; then, mechanically vibrating for 40-60 min at 400-500 Hz and 0.5-1.5 mm in amplitude; taking out the glass fiber, washing the glass fiber with acetone for 2 times, and drying the glass fiber at the temperature of 100-150 ℃ for 60-90 min;
d. d, immersing the glass fiber dried in the step c into the mixed solution, performing ultrasonic treatment for 25-30 min at the frequency of 20-30 KHz, and standing for 50-60 min; then, mechanically vibrating for 40-60 min at a frequency of 300-400 Hz and an amplitude of 0.5-1.5 mm; taking out the glass fiber, washing the glass fiber with acetone for 2 times, and drying the glass fiber at the temperature of 100-150 ℃ for 60-90 min;
e. plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; and d, dipping the glass fiber dried in the step d in the melt of PPE resin, wherein the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out the glass fiber from a creel, adjusting the tension through a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fiber in the die head, controlling the content of the fiber through the fiber outlet of the die head, cooling and solidifying, and cutting into pretreated glass fiber with the length of 8-10 mm through a granulator.
In the present invention, the nylon is any one of nylon 46, nylon 6, and nylon 6/nylon 66.
In the invention, the antioxidant is a phosphite antioxidant and an amine antioxidant, and the proportion of the components is 1: 1; the lubricant is pentaerythritol stearate; the heat stabilizer is a mixture of a sterically hindered phenol antioxidant and phosphate; the nucleating agent is calcium carboxylate CAV102 with long carbon chain as main component.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
1) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
2) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
3) and (3) respectively feeding the mixture obtained in the step 2) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 210-300 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
The invention has the following excellent effects:
the alcoholysis-resistant nylon composite material prepared by the invention is prepared by taking nylon, pretreated glass fiber, an auxiliary agent and the like as main materials and extruding and blending the main materials through a double-screw extruder on the premise of not adding an alcoholysis-resistant hydrolysis-resistant agent, and has the characteristics of high mechanical property, high heat resistance and excellent hydrolysis and alcoholysis resistance. The pretreated glass fiber is adsorbed with silane coupling agent and is impregnated with PPE melt, so that the glass fiber has excellent alcoholysis resistance, and the alcoholysis resistance of the glass fiber can be improved without reducing the physical properties of the nylon composite material; the nylon composite material has excellent alcoholysis resistance meeting the TL-VW774 test requirement, and the surface of a sample is good and unchanged and does not crack; not only solves the problem that alcoholysis resistance agent or alcoholysis resistance agent needs to be added to meet the alcoholysis resistance requirement in the prior art, but also solves the problem that mechanical property of a base material is obviously reduced after PPE is added in the prior art.
Detailed Description
The following examples are intended to describe the invention in detail, but the invention is not limited to these examples.
Example 1
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: 658.1% of nylon, 40% of pretreated glass fiber, 0.5% of nucleating agent, 0.5% of antioxidant, 0.6% of lubricant and 0.3% of heat stabilizer.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent =30:8:0.8, wherein the silane coupling agent is 3-aminopropyltriethoxysilane;
b. immersing common continuous glass fiber into the mixed solution, performing ultrasonic treatment for 20min at the frequency of 70KHz, and standing for 50 min; then mechanically vibrating for 40min, with the frequency of 600Hz and the amplitude of 0.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 150 deg.C for 90 min;
c. b, immersing the glass fiber dried in the step b into the mixed solution, performing ultrasonic treatment for 30min at the frequency of 40KHz, and standing for 50 min; then mechanically vibrating for 40min, with frequency 500Hz and amplitude 1 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 125 deg.C for 75 min;
d. d, immersing the glass fiber dried in the step c into the mixed solution, performing ultrasonic treatment for 28min, wherein the frequency is 20KHz, and standing for 50 min; then mechanically vibrating for 40min, with the frequency of 300Hz and the amplitude of 0.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 100 deg.C for 90 min;
e. plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; and d, dipping the glass fiber dried in the step d in the melt of PPE resin, wherein the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out glass fibers from a creel, adjusting the tension by a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fibers in the die head, controlling the content of the fibers through the fiber outlet of the die head, cooling and solidifying, and cutting the fibers into pretreated glass fibers with the length of 8-10 mm by a granulator;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 210-280 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
Example 2
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: 4658.5% of nylon, 40% of pretreated glass fiber, 0.1% of nucleating agent, 0.4% of antioxidant, 0.6% of lubricant and 0.4% of heat stabilizer.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent = 35: 10: 0.5, wherein the silane coupling agent is N-2-aminoethyl-3-aminopropyltrimethoxysilane;
b. immersing common continuous glass fiber into the mixed solution, performing ultrasonic treatment for 18min at the frequency of 75KHz, and standing for 60 min; then mechanically vibrating for 50min, with frequency 500Hz and amplitude 1.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 125 deg.C for 75 min;
c. b, immersing the glass fiber dried in the step b into the mixed solution, performing ultrasonic treatment for 28min, wherein the frequency is 45KHz, and standing for 60 min; then mechanically vibrating for 50min, with the frequency of 450Hz and the amplitude of 1.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 100 deg.C for 90 min;
d. d, immersing the glass fiber dried in the step c into the mixed solution, performing ultrasonic treatment for 25min, wherein the frequency is 25KHz, and standing for 60 min; then mechanically vibrating for 50min, with the frequency of 350Hz and the amplitude of 1 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 150 deg.C for 75 min;
e. plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; and d, dipping the glass fiber dried in the step d in the melt of PPE resin, wherein the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out glass fibers from a creel, adjusting the tension by a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fibers in the die head, controlling the content of the fibers through the fiber outlet of the die head, cooling and solidifying, and cutting the fibers into pretreated glass fibers with the length of 8-10 mm by a granulator;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 280-300 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
Example 3
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: nylon 6/nylon 6658.3%, pretreated glass fiber 40%, nucleating agent 0.4%, antioxidant 0.3%, lubricant 0.7% and heat stabilizer 0.3%.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent = 40: 5: 1, wherein the silane coupling agent is diethylenetriaminopropyltrimethoxysilane;
b. immersing common continuous glass fiber into the mixed solution, performing ultrasonic treatment for 15min at the frequency of 80KHz, and standing for 55 min; then mechanically vibrating for 60min, with the frequency of 550Hz and the amplitude of 1 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 100 deg.C for 60 min;
c. b, immersing the glass fiber dried in the step b into the mixed solution, performing ultrasonic treatment for 25min, wherein the frequency is 50KHz, and standing for 55 min; then mechanically vibrating for 60min, with frequency 500Hz and amplitude 0.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 150 deg.C for 60 min;
d. d, immersing the glass fiber dried in the step c into the mixed solution, performing ultrasonic treatment for 30min at the frequency of 30KHz, and standing for 55 min; then mechanically vibrating for 60min, with the frequency of 400Hz and the amplitude of 1.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 125 deg.C for 60 min;
e. plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; and d, dipping the glass fiber dried in the step d in the melt of PPE resin, wherein the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out glass fibers from a creel, adjusting the tension by a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fibers in the die head, controlling the content of the fibers through the fiber outlet of the die head, cooling and solidifying, and cutting the fibers into pretreated glass fibers with the length of 8-10 mm by a granulator;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 210-280 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
Example 4
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: nylon 6/nylon 6658.1%, pretreated glass fiber 40%, nucleating agent 0.5%, antioxidant 0.5%, lubricant 0.5%, and heat stabilizer 0.4%.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent = 40: 5: 1, wherein the silane coupling agent is diethylenetriaminopropyltrimethoxysilane;
b. soaking common continuous glass fiber in the mixed solution, performing ultrasonic treatment for 15min at frequency of 80KHz, and standing for 55 min; then mechanically vibrating for 60min, with the frequency of 550Hz and the amplitude of 1 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 100 deg.C for 60 min;
c. plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; and c, impregnating the glass fiber dried in the step b with a melt of PPE resin, wherein the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out glass fibers from a creel, adjusting the tension by a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fibers in the die head, controlling the content of the fibers through the fiber outlet of the die head, cooling and solidifying, and cutting the fibers into pretreated glass fibers with the length of 8-10 mm by a granulator;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 210-280 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
Example 5
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: nylon 4663%, pretreated glass fiber 35%, nucleating agent 0.5%, antioxidant 0.5%, lubricant 0.5%, and heat stabilizer 0.5%.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent = 35: 10: 0.5, wherein the silane coupling agent is N-2-aminoethyl-3-aminopropyltrimethoxysilane;
b. immersing common continuous glass fiber into the mixed solution, performing ultrasonic treatment for 18min at the frequency of 75KHz, and standing for 60 min; then mechanically vibrating for 50min, with frequency 500Hz and amplitude 1.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 125 deg.C for 75 min; this step was repeated 5 times;
c. plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; and c, impregnating the glass fiber dried in the step b with a melt of PPE resin, wherein the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out glass fibers from a creel, adjusting the tension by a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fibers in the die head, controlling the content of the fibers through the fiber outlet of the die head, cooling and solidifying, and cutting the fibers into pretreated glass fibers with the length of 8-10 mm by a granulator;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 280-300 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
Comparative example 1
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: 4658.5% of nylon, 40% of pretreated glass fiber, 0.1% of nucleating agent, 0.4% of antioxidant, 0.6% of lubricant and 0.4% of heat stabilizer.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution, wherein the volume ratio of the ethanol to the water to the silane coupling agent is ethanol: water: silane coupling agent = 35: 10: 0.5, wherein the silane coupling agent is N-2-aminoethyl-3-aminopropyltrimethoxysilane;
b. immersing common continuous glass fiber into the mixed solution, performing ultrasonic treatment for 18min at the frequency of 75KHz, and standing for 60 min; then mechanically vibrating for 50min, with frequency 500Hz and amplitude 1.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 125 deg.C for 75 min;
c. b, immersing the glass fiber dried in the step b into the mixed solution, performing ultrasonic treatment for 28min, wherein the frequency is 45KHz, and standing for 60 min; then mechanically vibrating for 50min, with the frequency of 450Hz and the amplitude of 1.5 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 100 deg.C for 90 min;
d. d, immersing the glass fiber dried in the step c into the mixed solution, performing ultrasonic treatment for 25min, wherein the frequency is 25KHz, and standing for 60 min; then mechanically vibrating for 50min, with the frequency of 350Hz and the amplitude of 1 mm; taking out the glass fiber, washing with acetone for 2 times, and drying at 150 deg.C for 75 min;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 280-300 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
Comparative example 2
The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight: nylon 6/nylon 6658.3%, pretreated glass fiber 40%, nucleating agent 0.4%, antioxidant 0.3%, lubricant 0.7% and heat stabilizer 0.3%.
The processing method of the alcoholysis-resistant nylon composite material for the automobile comprises the following steps:
(1) the glass fiber is pretreated, and the method comprises the following steps: plasticizing and melting PPE resin at 275-285 ℃ to obtain PPE resin melt; ordinary continuous glass fiber is impregnated by the melt of PPE resin, and the mass ratio of the glass fiber to the PPE resin is 1: 0.5. leading out glass fibers from a creel, adjusting the tension by a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the fibers in the die head, controlling the content of the fibers through the fiber outlet of the die head, cooling and solidifying, and cutting the fibers into pretreated glass fibers with the length of 8-10 mm by a granulator;
(2) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
(3) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
(4) and (3) respectively feeding the mixture obtained in the step (3) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 210-280 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
The tensile strength was measured according to ASTM-D638, the specimen type was type I, the specimen size (mm): (165. + -.2) × (12.70. + -. 0.2) × (3.20. + -. 0.2), and the drawing speed was 50 mm/min.
Flexural strength and flexural modulus were examined according to ASTM-D790, specimen size (mm): (127. + -. 2) × (12.7. + -. 0.2) × (3.20. + -. 0.2), and the bending speed was 13 mm/min.
Hydrolysis resistance and alcoholysis resistance are tested as follows: immersing the samples into a constant-temperature oil bath pot filled with a solution prepared according to the mass ratio of ethylene glycol to water of 1:1, heating to 135 ℃, keeping for 144h, taking out a group of samples every 48h, observing the surface morphology of the samples, and testing the bending strength of the samples after corrosion.
Table 1 shows the hydrolysis and alcoholysis resistance of the nylon composite
TABLE 1 hydrolysis resistance alcoholysis test Performance of the prepared nylon composite
Alcoholysis resistance was tested according to TL-VW 774: immersing the sample in a constant-temperature oil bath pot filled with pure glycol solvent, heating to 135 ℃ and keeping for 48h, taking out the sample, immersing the sample in cold glycol solvent to naturally cool the sample, observing the surface form of the sample, and testing the bending strength of the sample after corrosion, wherein the test results are shown in Table 2.
TABLE 2 alcoholysis resistance test performance table for nylon composite material
The comparative example and the embodiment show that the alcoholysis resistance of the nylon composite material can be greatly improved by adopting the combination of ultrasonic vibration and mechanical vibration, pretreating the glass fiber by utilizing the silane coupling agent and the PPE melt, adding the glass fiber, continuously boiling the glass fiber in a 1:1 aqueous solution of ethylene glycol at 135 ℃ for 144 hours, still keeping the performance of the glass fiber to be more than 78%, keeping the surface of the glass fiber to be good, having extremely strong alcoholysis resistance and keeping good mechanical performance, solving the problem that the alcoholysis resistance or alcoholysis resistance needs to be added to meet the alcoholysis resistance requirement in the prior art, and also solving the problem that the mechanical performance of a matrix material is obviously reduced after PPE is added in the prior art. As can be seen from examples 2 and 5, the alcoholysis resistance and mechanical properties of the pretreated substrate are reduced by repeating the ultrasonic treatment and the mechanical vibration for too many times; as can be seen from examples 3 and 4, the alcoholysis resistance and mechanical properties of the resin are reduced by the repetition of the ultrasonic treatment and the mechanical vibration during the pretreatment and the incomplete treatment.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the present disclosure, and such equivalent changes and modifications also fall within the scope of the present invention defined by the appended claims.
Claims (8)
1. The alcoholysis-resistant nylon composite material for the automobile comprises the following components in percentage by weight:
58 to 63 percent of nylon resin
35-40% of pretreated glass fiber
0.1 to 0.5 percent of nucleating agent
0.3 to 0.5 percent of antioxidant
0.5 to 0.7 percent of lubricant
0.3-0.5% of a heat stabilizer; wherein,
the glass fiber is pretreated, and the method comprises the following steps:
a. firstly, mixing a silane coupling agent, water and ethanol to prepare a mixed solution;
b. dipping the common continuous glass fiber in the mixed solution, performing ultrasonic treatment for 15-20 min at the frequency of 70-80 KHz, and standing for 50-60 min; then, mechanically vibrating for 40-60 min at 500-600 Hz and 0.5-1.5 mm in amplitude; taking out the glass fiber, washing the glass fiber with acetone for 2 times, and drying the glass fiber at the temperature of 100-150 ℃ for 60-90 min;
c. b, soaking the continuous glass fiber dried in the step b in the mixed solution, performing ultrasonic treatment for 25-30 min at the frequency of 40-50 KHz, and standing for 50-60 min; then, mechanically vibrating for 40-60 min at 400-500 Hz and 0.5-1.5 mm in amplitude; taking out the glass fiber, washing the glass fiber with acetone for 2 times, and drying the glass fiber at the temperature of 100-150 ℃ for 60-90 min;
d. c, soaking the glass fiber dried in the step c in the mixed solution, performing ultrasonic treatment for 25-30 min at the frequency of 20-30 KHz, and standing for 50-60 min; then, mechanically vibrating for 40-60 min at a frequency of 300-400 Hz and an amplitude of 0.5-1.5 mm; taking out the glass fiber, washing the glass fiber with acetone for 2 times, and drying the glass fiber at the temperature of 100-150 ℃ for 60-90 min;
e. and (d) melting the PPE resin into a PPE melt, leading out the glass fiber dried in the step (d) from a creel, adjusting the tension through a tension roller, entering a melt impregnation die head, realizing the dispersion and infiltration of the glass fiber in the die head, cooling, solidifying and granulating to obtain the pretreated glass fiber.
2. The alcoholysis resistant nylon composite for automobiles of claim 1 wherein the nylon is any one of nylon 46, nylon 6/nylon 66.
3. The alcoholysis-resistant nylon composite material for the automobile as claimed in claim 1, wherein the antioxidant is a phosphite antioxidant and an amine antioxidant, and the component ratio of the antioxidant is 1: 1; the lubricant is pentaerythritol stearate; the heat stabilizer is a mixture of a sterically hindered phenol antioxidant and a phosphate.
4. The alcoholysis resistant nylon composite material for automobiles of claim 1, wherein the nucleating agent is calcium carboxylate CAV102 with long carbon chain as main component.
5. The alcoholysis resistant nylon composite material for automobiles of claim 1, wherein the silane coupling agent is selected from any one of 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane and diethylenetriaminopropyltrimethoxysilane.
6. The alcoholysis-resistant nylon composite material for automobiles of claim 1, wherein the volume ratio of ethanol to water to the silane coupling agent in the mixed solution is ethanol: water: silane coupling agent = (30-40): (5-10): (0.5 to 1).
7. The alcoholysis resistant nylon composite material for automobiles of claim 1, wherein the mass ratio of the glass fiber to the PPE resin in step e is 1: 0.5.
8. an alcoholysis resistant nylon composite for automobiles according to any of claims 1 to 7 wherein the process comprises the steps of:
1) respectively weighing nylon resin, pretreated glass fiber, a nucleating agent, a heat stabilizer, an antioxidant and a lubricant according to the weight percentage of each component in the formula;
2) adding the nylon resin, the nucleating agent, the heat stabilizer, the antioxidant and the lubricant into a high-speed stirrer, mixing for 15-20 min, and uniformly mixing;
3) and (3) respectively feeding the mixture obtained in the step 2) and the pretreated glass fibers into a co-rotating double-screw extruder through main feeding equipment and side feeding equipment, wherein the length-diameter ratio of screws is 40, the rotating speed is 200-300 r/min, the temperature is 210-300 ℃, and the mixture is melted, mixed, extruded, granulated and packaged.
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| CN106883604A (en) * | 2017-04-07 | 2017-06-23 | 深圳市华盈新材料有限公司 | Automobile modified heat resistant oxygen aging nylon and its preparation technology |
| CN107987519A (en) * | 2017-11-22 | 2018-05-04 | 杭州悦仕达新材料科技有限公司 | Nylon composite materials |
| CN114716821A (en) * | 2022-03-21 | 2022-07-08 | 江苏博云塑业股份有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
| CN115710429A (en) * | 2022-10-11 | 2023-02-24 | 青岛国恩科技股份有限公司 | Hydrolysis-resistant alcoholysis-resistant reinforced nylon material and preparation method thereof |
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| CN105086443A (en) * | 2015-09-01 | 2015-11-25 | 惠州市华聚塑化科技有限公司 | Nylon composite material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883604A (en) * | 2017-04-07 | 2017-06-23 | 深圳市华盈新材料有限公司 | Automobile modified heat resistant oxygen aging nylon and its preparation technology |
| CN107987519A (en) * | 2017-11-22 | 2018-05-04 | 杭州悦仕达新材料科技有限公司 | Nylon composite materials |
| CN114716821A (en) * | 2022-03-21 | 2022-07-08 | 江苏博云塑业股份有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
| CN114716821B (en) * | 2022-03-21 | 2024-02-02 | 江苏博云塑业股份有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
| CN115710429A (en) * | 2022-10-11 | 2023-02-24 | 青岛国恩科技股份有限公司 | Hydrolysis-resistant alcoholysis-resistant reinforced nylon material and preparation method thereof |
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