CN111732726A - High-fluidity body flame-retardant long-carbon-chain nylon and preparation method thereof - Google Patents
High-fluidity body flame-retardant long-carbon-chain nylon and preparation method thereof Download PDFInfo
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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Abstract
The invention discloses a high-fluidity body flame-retardant long-carbon-chain nylon and a preparation method thereof. The invention starts from the source, produces the long carbon chain nylon resin with high fluidity and body flame-retardant property, utilizes the molecular assembly design principle, designs from the molecular structure, embeds the molecular chain structure which can improve the product flowing property and the self flame-retardant property on the molecular chain structure of the long carbon chain nylon, thereby obtaining the long carbon chain nylon product with high flowing body flame-retardant property.
Description
Technical Field
The invention relates to high-fluidity body flame-retardant long-carbon-chain nylon and a preparation method thereof, belonging to the field of polymer chemistry.
Background
The long carbon chain nylon is used as a special nylon in high-performance engineering plastics, has low water absorption rate, high toughness, dimensional stability, wear resistance, low-temperature impact resistance and the like due to a long molecular chain structure, and can be widely applied to the fields of machinery, automobiles, wires and cables, aviation, electronic and electric appliances, information, textile and the like. However, due to the long molecular chain structure of the polymer, molecular polymerization is difficult to control under high temperature and high pressure conditions, random polymerization is mostly adopted, the molecular structure is mostly reticular, molecular chain winding is complex, fine structures are rarely researched, and the requirements on different performances, such as high fluidity, high viscosity, flame retardance and the like, can only be groped by virtue of production experience or later-stage modification research is carried out to meet market requirements.
In the prior art, the existing material is usually modified at a later stage, for example, patent CN201710385026.6 discloses a high thermal conductivity high glow wire halogen-free flame retardant nylon composite material and a preparation method thereof, which is to add aminosilane as a coupling agent for secondary modification on the basis of material synthesis after the material is formed.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides the high-fluidity flame-retardant long-carbon-chain nylon and the preparation method thereof. In the early-stage neutralization and salt formation process of long carbon chain nylon, monoamino silane is introduced to replace a small part of amine raw materials, and active amino groups carried in molecular chains and dibasic acid are neutralized, so that Si-O bonds are introduced into the molecular weight, and the flowability of the product is improved, and the flame retardant property of the material is improved.
A preparation method of high-fluidity body flame-retardant long-chain nylon comprises the following steps:
1) adding 40-50 parts of distilled water into a salt making kettle, adding 20-25 parts of diamine and 20-25 parts of dibasic acid into the kettle, starting to heat and stir, adding 10-12 parts of aminosilane, continuing to stir fully, starting heating to heat, stopping heating when the temperature is increased to 100-105 ℃, and continuing to stir until the salt solution is completely neutralized, clear and transparent, so as to obtain the salt solution;
2) adding the salt solution obtained in the step 1) into a polymerization kettle, adding 0.2-0.5 part of phosphorous acid, starting stirring, heating to 240-250 ℃ for melt copolymerization, maintaining the pressure for reaction for 3-5 hours when the pressure reaches 1.5MPa, then maintaining the temperature for exhausting to normal pressure, heating a die head to 255 ℃, and discharging to obtain the high-fluidity body flame-retardant long-carbon-chain nylon resin product.
Further, the diamine is one of hexamethylene diamine, decamethylene diamine, dodecane diamine, and 4,4' -subunit dicyclohexylamine.
Further, the dibasic acid is one of sebacic acid and dodecanoic acid.
Further, the aminosilane is one of r-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane and aminopropylmethyldimethoxysilane.
Further, the antioxidant is phosphorous acid.
The application also protects the high-flow body flame-retardant long-chain nylon prepared by the preparation method.
The preparation principle of the high-fluidity body flame-retardant long-carbon-chain nylon comprises the following steps: the long carbon chain nylon is polymerized by neutralizing long carbon chain diacid and diamine to form salt, then performing dehydration polycondensation reaction under the conditions of high temperature and high pressure, and controlling the viscosity of the product by adding different types and different amounts of molecular weight regulators in the molecular polymerization process. The invention introduces part of amino silane in the raw material to replace part of diamine, because the amino silane surface has active group amino group, it can neutralize with carboxyl at one end of dibasic acid, at the same time, its molecular chain structure is different from diamine, and it has obvious steric hindrance in the high temperature polymerization process, it can effectively control the cross-linking between long carbon chain nylon molecular chains, thus it can further reduce the product viscosity; in addition, Si belongs to IVA group in the periodic table of elements and has certain flame retardant function, thereby improving the flame retardant effect of the long carbon chain nylon
Has the advantages that:
(1) the invention aims to produce the high-fluidity long-carbon-chain nylon resin with the flame-retardant body from the source, and utilizes the molecular assembly design principle to design from the molecular structure, and the molecular chain structure capable of improving the flow performance of the product and the flame-retardant performance of the product is embedded in the molecular chain structure of the long-carbon-chain nylon, so that the high-fluidity long-carbon-chain nylon product with the flame-retardant body is obtained.
(2) Part of aminosilane is used as a raw material, the long carbon chain nylon molecular chain is reassembled, the viscosity of the product is reduced through a molecular steric effect, and the fluidity of the product is improved;
(3) Si-O bonds are introduced into molecules, so that the original single C-H-N element system is changed, the flame retardant property of the product is improved, and the water resistance of the product is not influenced;
(4) the initial combination of the long carbon chain nylon and the organic silicon product is realized, and the double-sided characteristics of the long carbon chain nylon and the organic silicon product are exerted in the high-fluidity application field.
(5) The high-fluidity flame-retardant long-carbon-chain nylon resin prepared by the invention improves the fluidity and the flame retardance of the product from the aspect of molecular structure, and guides the direction for researching the refinement of the copolymerization modification of high polymer materials in the future.
Detailed Description
In order to make the technical solutions in the present application better understood, the present invention is further described below with reference to examples, which are only a part of examples of the present application, but not all examples, and the present invention is not limited by the following examples.
Example 1
Adding 50 parts of distilled water into a salt preparation kettle, then adding 34 parts of decamethylenediamine and 50 parts of dodecanoic acid into the kettle, fully stirring, adding 11 parts of r-aminopropyltriethoxysilane, heating and stirring to 100 ℃, stopping heating, and continuing stirring until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 245 ℃ for melt copolymerization, maintaining pressure for reaction for 5 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, pulling strips, discharging, and granulating to obtain the high-fluidity flame-retardant long-carbon-chain nylon 1012 resin.
The production process of the traditional nylon 1012 resin comprises the following steps: 50 parts of distilled water is added into a salt making kettle, 44 parts of decamethylene diamine and 50 parts of dodecanoic acid are added into the kettle, the temperature is increased to 100 ℃, the heating is stopped, and the stirring is continued until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 245 ℃ for melt copolymerization, maintaining pressure for reaction for 5 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, pulling strips, discharging, and cutting into granules to obtain the nylon 1012 resin.
The performance data of the nylon 1012 resin of the present invention versus conventional homopolymer 1012 products produced using conventional processes are shown in Table 1:
table 1 comparison of data for nylon 1012 resin of the present invention and conventional resin
| Item | Conventional 1012 resin (same process) | Nylon 1012 resin of the invention |
| Appearance of the product | White translucent particles | White translucent particles |
| Melt flow Rate, g/10min | 15 | 21 |
| Flame retardant properties | Continuous combustion for 30S, and drop ignition | Extinguished in 30 and ignited by dripping |
| Water absorption,%, 24h | 0.33 | 0.34 |
Through the experimental comparison and analysis, on the premise of adopting the same production process, after r-aminopropyltriethoxysilane is introduced into a molecular chain, the appearance of a long carbon chain nylon 1012 resin product prepared by polymerization is still white semitransparent particles, and on the premise of consistent end capping quantity, the melt flow rate of the product is improved by 40 percent, so that the steric hindrance effect generated by silane molecules in the polymerization process is fully reflected, and the flowability of the product is obviously improved; the water absorption rate is not obviously changed, the flame combustion time can be self-extinguished within 30s, and the flame retardant property is obviously improved.
Example 2:
adding 50 parts of distilled water into a salt making kettle, then adding 29 parts of hexamethylene diamine and 45 parts of sebacic acid into the kettle, fully stirring, adding 10.5 parts of N-aminoethyl-3-aminopropylmethyldimethoxysilane, heating and stirring to 105 ℃, stopping heating, and continuing stirring until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 245 ℃ for melt copolymerization, maintaining pressure for reaction for 4 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, drawing strips, discharging, and cutting into granules to obtain the high-fluidity body flame-retardant long-carbon-chain nylon 610 resin.
The production process of the traditional nylon 610 resin by utilizing the traditional preparation process comprises the following steps: 50 parts of distilled water is added into a salt making kettle, 36.5 parts of hexamethylene diamine and 45 parts of sebacic acid are added into the kettle, the temperature is increased to 105 ℃, the heating is stopped, and the stirring is continued until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 245 ℃ for melt copolymerization, maintaining pressure for reaction for 4 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, drawing strips, discharging, and pelletizing to obtain the traditional nylon 610 resin.
The performance data of the nylon 610 resin of the present invention and the conventional homopolymer produced by the conventional production process are summarized in Table 2:
TABLE 2 comparison of data for nylon 610 resin of the present invention and conventional resin
| Item | Traditional nylon 610 resin (same process) | Nylon 610 resin of the invention |
| Appearance of the product | White translucent particles | White translucent particles |
| Melt flow Rate, g/10min | 21 | 34 |
| Flame retardant properties | 12s extinguishment and drop ignition | Extinguished within 10s and ignited by dripping |
| Water absorption,%, 24h | 1.42 | 1.47 |
The comparative test data shows that the appearance and the water absorption of the long carbon chain nylon 610 resin product prepared after the N-aminoethyl-3-aminopropylmethyldimethoxysilane is added have no obvious influence, but the fluidity of the product can be obviously improved, the melt flow rate is improved by 61.9 percent, and the method fully shows that the polymerization steric hindrance effect is obvious after the N-aminoethyl-3-aminopropylmethyldimethoxysilane is introduced, the possibility of molecular chain agglomeration is reduced, and the molecular weight of the product is reduced; due to the introduction of the Si element, the flame combustion time is shortened in the flame-retardant aspect, and the flame-retardant property of the product is improved.
Example 3:
adding 50 parts of distilled water into a salt preparation kettle, then adding 23 parts of hexamethylenediamine and 40 parts of dodecanoic acid into the kettle, fully stirring, adding 8 parts of aminopropyl methyl dimethylsilane, heating and stirring to 100 ℃, stopping heating, and continuing stirring until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 240 ℃ for melt copolymerization, maintaining pressure for reaction for 3 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, drawing strips, discharging, and cutting into granules to obtain the high-fluidity body flame-retardant long-carbon-chain nylon 612 resin.
Preparing nylon 612 resin by using a traditional process: 50 parts of distilled water is added into a salt making kettle, then 27 parts of hexamethylene diamine and 40 parts of dodecanoic acid are added into the kettle, the temperature is increased to 100 ℃, the heating is stopped, and the stirring is continued until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 240 ℃ for melt copolymerization, maintaining pressure for reaction for 3 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, drawing strips, discharging, and pelletizing to obtain the traditional nylon 612 resin.
The performance data of the nylon 612 resin of the present invention and the conventional homopolymer produced by the conventional production process are summarized in Table 3:
TABLE 3 comparison of data for nylon 612 resin of the present invention and conventional resins
| Item | Traditional nylon 612 resin (same process) | Nylon 612 resin for use in the present invention |
| Appearance of the product | White translucent particles | White translucent particles |
| Melt flow Rate, g/10min | 25 | 36 |
| Flame retardant properties | 12s extinguishment and drop ignition | Extinguished within 10s and ignited by dripping |
| Water absorption,%, 24h | 1.35 | 1.40 |
On the premise that the production process for producing the long-carbon-chain nylon 612 is not changed, aminopropyl methyl dimethylsilane is used for replacing part of ethylenediamine to participate in the polymerization of the product, the comparative test data show that the introduction of silane molecules still has no obvious influence on the appearance and the water absorption of the product, but the fluidity of the product can be greatly improved, the melt flow rate of the long-carbon-chain nylon 612 resin can be improved by 44%, the flame-retardant effect is improved to be self-extinguished within 10s from the original flame burning extinguishment of 12s on average, and the polymerization degree of molecular polycondensation and the flame-retardant effect of the introduced elements are fully reduced by the steric effect existing after the introduction of the silane molecules.
Example 4:
adding 50 parts of distilled water into a salt making kettle, then adding 50 parts of dodecadiamine and 40 parts of dodecanoic acid into the kettle, fully stirring, adding 12 parts of r-aminopropyltriethoxysilane, heating and stirring to 100 ℃, stopping heating, and continuing stirring until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 245 ℃ for melt copolymerization, maintaining pressure reaction for 5 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, pulling strips, discharging, and granulating to obtain the high-fluidity flame-retardant long-carbon-chain nylon 1212 resin.
Preparation of nylon 1212 resin using conventional process: 50 parts of distilled water is added into a salt making kettle, then 60 parts of dodecadiamine and 40 parts of dodecanoic acid are added into the kettle, the temperature is raised and the stirring is carried out to 100 ℃, the heating is stopped, and the stirring is continued until the salt solution is completely neutralized, clarified and transparent. And adding the obtained salt solution into a polymerization kettle, adding 0.1 part of phosphorous acid, starting stirring after vacuum opening, heating to 245 ℃ for melt copolymerization, maintaining pressure reaction for 5 hours when the pressure reaches 1.5MPa, then maintaining the temperature and exhausting to normal pressure, heating a die head to about 255 ℃, drawing strips, discharging, and pelletizing to obtain the traditional nylon 1212 resin.
The performance data of the nylon 1212 resin of the present invention and the conventional homopolymer produced by the same production process are summarized in Table 4:
TABLE 4 comparison of data for nylon 1212 resin of the present invention and conventional resin
| Item | Traditional nylon 1212 resin (same process) | Nylon 1212 resin for use in the present invention |
| Appearance of the product | White translucent particles | White translucent particles |
| Melt flow rate, Mpa | 18 | 29 |
| Flame retardant properties | Continuous combustion for 30S, and drop ignition | Extinguished in 30 and ignited by dripping |
| Water absorption,%, 24h | 0.26 | 0.28 |
Compared with the traditional production process, the long carbon chain nylon 1012 product prepared by the invention has the advantages that the water absorption rate is basically unchanged, the melt flow rate is greatly improved, the flame retardant property of the product is self-extinguished within 30 seconds after the original continuous combustion, and the flame retardant effect is obviously improved.
Claims (6)
1. A preparation method of high-fluidity body flame-retardant long-chain nylon is characterized by comprising the following steps:
1) adding 40-50 parts of distilled water into a salt making kettle, adding 20-25 parts of diamine and 20-25 parts of dibasic acid into the kettle, starting to heat and stir, adding 10-12 parts of aminosilane, continuing to stir fully, starting heating to heat, stopping heating when the temperature is increased to 100-105 ℃, and continuing to stir until the salt solution is completely neutralized, clear and transparent, so as to obtain the salt solution;
2) adding the salt solution obtained in the step 1) into a polymerization kettle, adding 0.2-0.5 part of phosphorous acid, starting stirring, heating to 240-250 ℃ for melt copolymerization, maintaining the pressure for reaction for 3-5 hours when the pressure reaches 1.5MPa, then maintaining the temperature for exhausting to normal pressure, heating a die head to 255 ℃, and discharging to obtain the high-fluidity body flame-retardant long-carbon-chain nylon resin product.
2. The method of claim 1, wherein the diamine is one of hexamethylene diamine, decamethylene diamine, dodecane diamine, and 4,4' -ylidenedicyclohexylamine.
3. The method of claim 1, wherein the dibasic acid is one of sebacic acid and dodecanoic acid.
4. The method according to claim 1, wherein the aminosilane is one selected from the group consisting of r-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and aminopropylmethyldimethylsilane.
5. The method of claim 1, wherein the antioxidant is phosphorous acid.
6. A high flow bulk flame retardant long chain nylon prepared by the preparation method of any one of claims 1 to 5.
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| CN111732726B CN111732726B (en) | 2022-04-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012678A1 (en) * | 1999-08-13 | 2001-02-22 | Solutia Inc. | Methods for the preparation of polyamide nanocomposite compositions by in situ polymerization |
| CN1493602A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Long carbon chain nylon and its synthesis method |
| CN107286340A (en) * | 2017-07-27 | 2017-10-24 | 株洲时代新材料科技股份有限公司 | A kind of copolymerization transparent nylon and preparation method thereof |
| WO2018010206A1 (en) * | 2016-07-12 | 2018-01-18 | 江门市德众泰工程塑胶科技有限公司 | Aromatic polyamide composite for use in electroplating treatment and preparation method therefor |
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2020
- 2020-06-19 CN CN202010564700.9A patent/CN111732726B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012678A1 (en) * | 1999-08-13 | 2001-02-22 | Solutia Inc. | Methods for the preparation of polyamide nanocomposite compositions by in situ polymerization |
| CN1493602A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Long carbon chain nylon and its synthesis method |
| WO2018010206A1 (en) * | 2016-07-12 | 2018-01-18 | 江门市德众泰工程塑胶科技有限公司 | Aromatic polyamide composite for use in electroplating treatment and preparation method therefor |
| CN107286340A (en) * | 2017-07-27 | 2017-10-24 | 株洲时代新材料科技股份有限公司 | A kind of copolymerization transparent nylon and preparation method thereof |
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