CN112592583A - Alcoholysis-resistant enhanced PA6T material and preparation method thereof - Google Patents
Alcoholysis-resistant enhanced PA6T material and preparation method thereof Download PDFInfo
- Publication number
- CN112592583A CN112592583A CN202011278992.6A CN202011278992A CN112592583A CN 112592583 A CN112592583 A CN 112592583A CN 202011278992 A CN202011278992 A CN 202011278992A CN 112592583 A CN112592583 A CN 112592583A
- Authority
- CN
- China
- Prior art keywords
- alcoholysis
- pa6t
- resistance enhanced
- material according
- pa6t material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- 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
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an alcoholysis-resistant reinforced PA6T material and a preparation method thereof, wherein the material comprises, by mass, 38.4-64.4 parts of high-temperature nylon, 30-50 parts of reinforced fibers, 5-10 parts of a compatilizer, 0.2-0.5 part of a heat stabilizer, 0.2-0.5 part of an antioxidant and 0.2-0.6 part of a lubricant, wherein the compatilizer is a styrene-N-phenylmaleimide copolymer, can capture alcohol substances invading the material, plays a role in active defense, improves the binding power between glass and matrix resin, and enables the material to have good alcoholysis resistance. The preparation method is simple and has strong industrial practicability.
Description
Technical Field
The invention belongs to the technical field of plastic materials for engines, and particularly relates to an alcoholysis-resistant reinforced PA6T material and a preparation method thereof.
Background
The cooling system is an important component of the engine system and its function is to ensure that the engine operates in the proper temperature range. At present, a water-cooling system is generally adopted, and cooling liquid is driven by a water pump and takes away redundant heat of an engine through parts such as the water pump, an engine cooling water jacket, a radiator, a thermostat, a cold air system connecting pipeline and the like. The main plastic parts of the cooling system comprise a water tank, a radiator water chamber, a thermostat shell, a water pump impeller and a throttle valve, and the plastic parts are in long-term contact with cooling liquid in the use process and require good performance of resisting the cooling liquid. The main components of the refrigerating fluid are 1:1 of ethylene glycol and water, and researches show that the ethylene glycol can induce H bond breakage between nylon amido bonds, and the ethylene glycol and hydroxyl in the ethylene glycol form a new H bond, so that the nylon is plasticized, chain breakage is induced, and the adhesive force of an interface between glass fibers and nylon resin is reduced. At present, a cooling system mainly adopts PA66+ 30% glass fiber, the working temperature of an engine is higher and higher along with the improvement of the heat efficiency of the engine, the efficiency requirement of the cooling system is severer day by day, the vitrification temperature of PA66 is low at high temperature, the material strength is insufficient, the material is easy to corrode by ethylene glycol, and the requirement of future automobile products cannot be met. PA6T has very high glass transition temperature and melting point and can well meet the requirements of cooling system materials, but PA6T also has very high amido bond density, researches show that the tensile strength retention rate of PA6T is only 35% after soaking in ethanol at 23 ℃ for 168h, and various automobile manufacturers generally require that the tensile strength retention rate is more than 40% or more than 40MPa after soaking in refrigerating fluid at the temperature of more than 130 ℃ for 1000 h. In the prior art, a polyamine hydrolysis resistant agent is generally added to react with a nylon terminal carboxyl group, a metal halide and an amide group are added to form a complex structure to stabilize a nylon molecular chain, a coupling agent and an ethylene-octene copolymer grafted maleic acid rod POE-G-MAH are added to improve the adhesive force between glass fiber and matrix resin and use special hydrolysis resistant glass fiber, but the polyamine and the metal halide are expensive, glycol invading the material is not actively captured, the coupling agent is not temperature-resistant, the coupling agent is easy to lose efficacy at high temperature and cannot effectively couple, and the PEO-G-MAH can reduce the glass transition temperature of the material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an alcoholysis resistance enhanced PA6T material and a preparation method thereof, and solves the problem of alcoholysis resistance of plastic parts of engines in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides an alcoholysis-resistant reinforced PA6T material, which comprises the following components in parts by mass:
wherein the high-temperature nylon is at least one of poly (hexamethylene terephthalate), an isophthalic acid hexamethylene diamine copolymer, poly (hexamethylene terephthalate) and a 2-methyl-1, 5-pentanediamine copolymer; the compatilizer is a styrene-N-phenylmaleimide copolymer, and the reinforcing fiber is hydrolysis-resistant glass fiber.
In a preferred embodiment of the present invention, the molecular formula of the compatibilizer is
Wherein the NPMI content is 30-35 wt%, the Sty content is 55-68 wt%, the MAH content is 2-10 wt%, and the molecular weight is 2 x 10^ 104-3*10^4In the meantime.
In a preferred embodiment of the present invention, the glass transition temperature of the compatibilizer is 196 ℃ and the thermal decomposition temperature is 350 ℃.
In a preferred embodiment of the invention, the high-temperature nylon is nylon with the characteristic viscosity of 0.6-1.0 dL/g.
In a preferred embodiment of the invention, the surface of the reinforcing fiber at least contains 0.5 wt% of maleic stem grafted or copolymerized polyolefin fiber emulsifier.
In a preferred embodiment of the present invention, the diameter of the reinforcing fiber is 11 to 12 μm, and the chopped length is 3 to 4.5 mm.
In a preferred embodiment of the present invention, the thermal stabilizer is bis (2,2,6, 6-tetramethyl-3-piperidinylamino) -isophthalamide (SEED).
In a preferred embodiment of the invention, the antioxidant is 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane (9228).
In a preferred embodiment of the present invention, the lubricant is one or more of a modified high molecular weight silicone lubricant and an ethylene acrylic acid copolymer.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the alcoholysis resistance enhanced PA6T material comprises the following steps:
1) uniformly mixing high-temperature nylon, a compatilizer, a heat stabilizer, an antioxidant and a lubricant in parts by mass to obtain a premix;
2) adding the premix into a double-screw extruder, and adding the reinforced fibers from a side feed in parts by mass, wherein the double-screw extruder adopts a medium-strength screw, and the length-diameter ratio of the medium-strength screw is 40-44: 1, extruding at the temperature of 280-320 ℃ and at the rotating speed of 350-500r/min to obtain the alcoholysis resistance enhanced PA6T material.
Compared with the background technology, the technical scheme has the following advantages:
according to the invention, PA6T/6I, PA6T/DT with high glass transition temperature is matched with styrene-N-phenylmaleimide copolymer with high glass transition temperature, high temperature resistance and high maleic anhydride content, and phenyl maleimide and maleic anhydride in the styrene-N-phenylmaleimide copolymer are used for capturing alcohol substances in an invasive material, so that compared with the prior art, the active defense effect is achieved, and the binding power between glass and matrix resin can be improved; meanwhile, the styrene-N-phenylmaleimide copolymer has the decomposition temperature of 350 ℃ suitable for high-temperature processing, is matched with the processing temperature of high-temperature nylon, and has good industrial practicability.
Detailed Description
In the following examples or comparative example preparation processes, firstly, weighing the high-temperature nylon, the compatilizer, the heat stabilizer, the antioxidant and the lubricant according to the following table 1, and uniformly mixing in a low-speed mixer; and then, adding the premix into a double-screw extruder, adding the reinforced fibers from a side feed according to a mass ratio, wherein the double-screw extruder with a medium-strength screw is adopted, and the length-diameter ratio is 40-44: 1, the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min; wherein the diameter of the reinforced fiber is 11 microns, the chopped length is 3-4.5mm, and the reinforced fiber is quantitatively fed from a 5 th barrel by a weight loss metering device.
TABLE 1 ingredient tables for examples 1-3 and comparative examples 1-3
The nylon materials prepared in the above examples 1 to 3 and comparative examples 1 to 3 were tested, and the results are shown in the following table 2:
TABLE 2 Performance test results for examples 1-3 and comparative examples 1-3
Compared with the comparative example 1, the embodiment 1 shows that the alcoholysis resistance of the material can be obviously improved by adding the styrene-N-phenylmaleimide copolymer, the styrene-N-phenylmaleimide copolymer has high decomposition temperature and is suitable for high-temperature processing, the styrene-N-phenylmaleimide copolymer contains a large amount of anhydride functional groups, the bonding force between glass fibers and matrix resin can be improved, meanwhile, unreacted anhydride functional groups can react with invaded glycol to generate esters, the esters play a role of alcohol capture agents, the glass transition temperature is high, molecular chain segments are still in a frozen state at 130 ℃, and the glycol is not easy to enter the material; compared with the comparative example 2, the effect of adding the styrene-N-phenylmaleimide copolymer is obviously better than that of adding the POE-G-MAH, on one hand, the anhydride content of the POE-G-MAH is low, and the grafting rate is only 0.5-1.5 percent, and on the other hand, the glass transition temperature of the material is reduced by adding the POE-G-MAH, so that the alcoholysis resistance of the material at high temperature is greatly reduced; comparison of example 1 with comparative example 3 shows that PA6T/6I has a glass transition temperature of more than 135 ℃ and a glass transition temperature significantly higher than that of PA 6665 ℃ and, although having a lower crystallinity than PA66, has an alcoholysis resistance which is significantly better than that of PA66, especially at high temperatures.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An alcoholysis resistance enhanced PA6T material, which is characterized in that: the adhesive comprises the following components in parts by mass:
wherein the high-temperature nylon is at least one of poly (hexamethylene terephthalate), an isophthalic acid hexamethylene diamine copolymer, poly (hexamethylene terephthalate) and a 2-methyl-1, 5-pentanediamine copolymer; the compatilizer is a styrene-N-phenylmaleimide copolymer, and the reinforcing fiber is hydrolysis-resistant glass fiber.
2. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the molecular formula of the compatilizer is
Wherein the NPMI content is 30-35 wt%, the Sty content is 55-68 wt%, and the MAH content is 2-10 wt%.
3. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the glass transition temperature of the compatilizer is 196 ℃, and the thermal decomposition temperature is 350 ℃.
4. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the high-temperature nylon adopts nylon with the intrinsic viscosity of 0.6-1.0 dL/g.
5. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the surface of the reinforcing fiber at least contains 0.5 wt% of maleic stem grafted or copolymerized polyolefin fiber emulsifier.
6. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the diameter of the reinforcing fiber is 11-12 mu m, and the chopped length is 3-4.5 mm.
7. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the heat stabilizer is bis (2,2,6, 6-tetramethyl-3-piperidyl amido) -isophthalamide.
8. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the antioxidant is 3, 9-di (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
9. An alcoholysis resistance enhanced PA6T material according to claim 1, wherein: the lubricant is one or more of modified high molecular weight organic silicon lubricant and ethylene acrylic acid copolymer.
10. The method for preparing the alcoholysis resistance enhanced PA6T material as claimed in any one of claims 1 to 9, wherein the steps of: the method comprises the following steps:
1) uniformly mixing high-temperature nylon, a compatilizer, a heat stabilizer, an antioxidant and a lubricant in parts by mass to obtain a premix;
2) adding the premix into a double-screw extruder, and adding the reinforced fibers from a side feed in parts by mass, wherein the double-screw extruder adopts a medium-strength screw, and the length-diameter ratio of the medium-strength screw is 40-44: 1, extruding at the temperature of 280-320 ℃ and at the rotating speed of 350-500r/min to obtain the alcoholysis resistance enhanced PA6T material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011278992.6A CN112592583B (en) | 2020-11-16 | 2020-11-16 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011278992.6A CN112592583B (en) | 2020-11-16 | 2020-11-16 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112592583A true CN112592583A (en) | 2021-04-02 |
| CN112592583B CN112592583B (en) | 2023-03-10 |
Family
ID=75183016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011278992.6A Active CN112592583B (en) | 2020-11-16 | 2020-11-16 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112592583B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039719A (en) * | 1989-07-14 | 1991-08-13 | Monsanto Kasei Company | Glass fiber reinforced thermoplastic resin composition |
| CN101265359A (en) * | 2007-03-16 | 2008-09-17 | 上海普利特复合材料有限公司 | Conducting heat-resisting nylon/acrylonitrile-butadiene-styrene resin mixing material |
| CN102516761A (en) * | 2011-12-04 | 2012-06-27 | 上海金发科技发展有限公司 | Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof |
| CN104854192A (en) * | 2013-12-10 | 2015-08-19 | Lg化学株式会社 | Halogen-based flame-retardant glass fiber-reinforced polyamide resin composition, and method for preparing same |
| CN106433112A (en) * | 2016-10-09 | 2017-02-22 | 上海金发科技发展有限公司 | PA (polyamide)/AS (acrylonitrile-styrene) based resin compound and preparation method thereof |
| CN106751804A (en) * | 2016-12-29 | 2017-05-31 | 上海普利特复合材料股份有限公司 | A kind of high-performance composite materials as prepared by recovery waste carpet PA66 materials and preparation method thereof |
| CN108587151A (en) * | 2017-12-27 | 2018-09-28 | 浙江普利特新材料有限公司 | It is a kind of to apply in automobile cooling system alcoholysis resistance nylon material and preparation method thereof |
| CN109517373A (en) * | 2018-11-20 | 2019-03-26 | 安徽江淮汽车集团股份有限公司 | A kind of PA6/AES composite material and preparation method |
| CN109593356A (en) * | 2018-11-19 | 2019-04-09 | 江苏金发科技新材料有限公司 | PA66 composite material and preparation method with excellent low temperature toughness, low water absorption and high rigidity |
| CN110079084A (en) * | 2019-05-29 | 2019-08-02 | 辰东意普万新材料(广东)有限公司 | Nylon composite materials and preparation method thereof |
| CN111133038A (en) * | 2017-09-25 | 2020-05-08 | 东洋纺株式会社 | Molded article comprising semi-aromatic polyamide resin composition as component |
-
2020
- 2020-11-16 CN CN202011278992.6A patent/CN112592583B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039719A (en) * | 1989-07-14 | 1991-08-13 | Monsanto Kasei Company | Glass fiber reinforced thermoplastic resin composition |
| CN101265359A (en) * | 2007-03-16 | 2008-09-17 | 上海普利特复合材料有限公司 | Conducting heat-resisting nylon/acrylonitrile-butadiene-styrene resin mixing material |
| CN102516761A (en) * | 2011-12-04 | 2012-06-27 | 上海金发科技发展有限公司 | Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof |
| CN104854192A (en) * | 2013-12-10 | 2015-08-19 | Lg化学株式会社 | Halogen-based flame-retardant glass fiber-reinforced polyamide resin composition, and method for preparing same |
| CN106433112A (en) * | 2016-10-09 | 2017-02-22 | 上海金发科技发展有限公司 | PA (polyamide)/AS (acrylonitrile-styrene) based resin compound and preparation method thereof |
| CN106751804A (en) * | 2016-12-29 | 2017-05-31 | 上海普利特复合材料股份有限公司 | A kind of high-performance composite materials as prepared by recovery waste carpet PA66 materials and preparation method thereof |
| CN111133038A (en) * | 2017-09-25 | 2020-05-08 | 东洋纺株式会社 | Molded article comprising semi-aromatic polyamide resin composition as component |
| CN108587151A (en) * | 2017-12-27 | 2018-09-28 | 浙江普利特新材料有限公司 | It is a kind of to apply in automobile cooling system alcoholysis resistance nylon material and preparation method thereof |
| CN109593356A (en) * | 2018-11-19 | 2019-04-09 | 江苏金发科技新材料有限公司 | PA66 composite material and preparation method with excellent low temperature toughness, low water absorption and high rigidity |
| CN109517373A (en) * | 2018-11-20 | 2019-03-26 | 安徽江淮汽车集团股份有限公司 | A kind of PA6/AES composite material and preparation method |
| CN110079084A (en) * | 2019-05-29 | 2019-08-02 | 辰东意普万新材料(广东)有限公司 | Nylon composite materials and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112592583B (en) | 2023-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798456B (en) | Nylon material with star branched structure and preparation method thereof | |
| CN107298855B (en) | A kind of hydrolysis-resistant alcoholysis-resistant enhancing nylon material and preparation method thereof | |
| CN112266607A (en) | Heat-resistant glass fiber reinforced nylon material and preparation method thereof | |
| CN102516761A (en) | Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof | |
| CN102947392A (en) | Polyamide compositiions having high acid ends | |
| CN112694748A (en) | High-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and preparation method thereof | |
| CN106519659A (en) | A high-performance heat-conducting nylon composite material, a preparing method thereof and applications of the composite material | |
| WO2022014390A1 (en) | Crystalline polyamide resin, resin composition, and molded article | |
| CN106317629A (en) | PP-PA polymer alloy material and manufacturing method thereof | |
| CN114573981B (en) | Halogen-free flame-retardant PA/PPO composite material and preparation method thereof | |
| CN112592583B (en) | Alcoholysis-resistant enhanced PA6T material and preparation method thereof | |
| EP0741762B2 (en) | Polyamide resin composition and molding thereof | |
| CN105086443A (en) | Nylon composite material | |
| CN107674414A (en) | A kind of hydrolysis enhancing nylon material and preparation method thereof | |
| CN114410105A (en) | High-impact-resistance wear-resistant polyamide composition and preparation method and application thereof | |
| CN113861671A (en) | High-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and preparation method thereof | |
| CN108276746A (en) | A kind of liquid crystal polyester/nylon alloy material and preparation method thereof | |
| CN105062046A (en) | PPA composite material | |
| CN110079084A (en) | Nylon composite materials and preparation method thereof | |
| CN108264741A (en) | A kind of liquid crystal polyester/nylon composite materials and preparation method thereof | |
| CN114773727B (en) | Polypropylene composite material and preparation method and application thereof | |
| CN105860036A (en) | Liquid crystal polyester, molding composition composed of liquid crystal polyester and application of molding composition | |
| CN105860035A (en) | Liquid crystal polyester, molding composition composed of liquid crystal polyester and application of molding composition | |
| CN113292848A (en) | Hydrolysis-resistant glass fiber reinforced polyamide composite material and preparation method thereof | |
| CN109161190B (en) | Glass fiber reinforced PA66 automobile intake manifold material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |