CN109735103B - Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof - Google Patents
Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof Download PDFInfo
- Publication number
- CN109735103B CN109735103B CN201910033554.4A CN201910033554A CN109735103B CN 109735103 B CN109735103 B CN 109735103B CN 201910033554 A CN201910033554 A CN 201910033554A CN 109735103 B CN109735103 B CN 109735103B
- Authority
- CN
- China
- Prior art keywords
- parts
- preparation
- precipitation
- silicon dioxide
- melamine cyanurate
- 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.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a soaking precipitation-resistant halogen-free flame-retardant polyamide composite material and a preparation method thereof, wherein the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material is prepared from 65-90 parts by weight of polyamide, 8-25 parts by weight of silicon dioxide modified melamine cyanurate, 0.5-5 parts by weight of epoxy polysiloxane and 0.5-5 parts by weight of silicon dioxide modified melamine cyanurate; 0.1-1 part of antioxidant and 0.1-1 part of lubricant are extruded and granulated by a double screw to obtain the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material. The soaking precipitation-resistant halogen-free flame-retardant polyamide material prepared by the invention has the advantages of high flame-retardant efficiency, good toughness, soaking precipitation resistance, simple and convenient processing and the like, and is widely applied to the field of electronics and electricity.
Description
Technical Field
The invention relates to the technical field of polyamide composite materials, in particular to a soaking precipitation-resistant halogen-free flame-retardant polyamide composite material and a preparation method thereof.
Background
The polyamide as engineering plastic has the characteristics of high mechanical property, high impact property, high heat resistance, good chemical resistance, easy forming and the like, and is widely applied to the fields of automobiles, electronic and electric appliances and the like. However, the polyamide generates a droplet phenomenon in the combustion process, generates a large amount of flaming droplets, and easily causes secondary combustion. Therefore, the polyamide needs to be subjected to flame retardant modification during the use process.
Currently, flame retardant systems for polyamides are mainly bromine antimony systems, nitrogen systems, phosphorus nitrogen systems and inorganic mineral fillers. The bromine-antimony composite flame-retardant polyamide has excellent flame-retardant performance, and simultaneously maintains good processability and mechanical performance, but the bromine-antimony flame retardant generates a large amount of smoke and corrosive harmful gases during combustion, and the use of the flame retardant is limited. The phosphorus-nitrogen system halogen-free flame retardant can be compared favorably with the traditional bromine-antimony flame retardant, but the phosphorus-nitrogen system has high price and cannot be popularized and used in a large area.
Melamine Cyanurate (MCA) is used as a halogen-free flame retardant with high nitrogen content, has the advantages of high decomposition temperature, low smoke, no toxicity, low price and the like, and has become the first choice of halogen-free flame retardant in the application of halogen-free flame retardants. However, MCA as a filling type flame retardant has poor compatibility with polyamide, the mechanical property of the material is greatly reduced after the flame retardant is added, and the flame retardant is easy to migrate to the surface of the material after the material is placed for a long time, so that the surface of a product is frosted. Especially under the action of high temperature and high humidity, the precipitation rate of the flame retardant is accelerated, and the service performance of the product is influenced finally.
Chinese patent application publication No. CN 103897128A (application No. 201410158223.0) discloses a flame retardant polymeric MCA compound and a preparation method thereof, wherein melamine is subjected to graft modification, and then the melamine is reacted with cyanuric acid to generate a salt. The polymeric MCA reduces the precipitation rate of the flame retardant to a certain extent due to the increase of the molecular weight of the flame retardant.
Disclosure of Invention
The invention aims to overcome the defects of the MCA flame-retardant polyamide preparation technology and provides a soaking precipitation-resistant halogen-free flame-retardant polyamide composite material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material is composed of the following materials in parts by weight:
65-90 parts of polyamide;
8-25 parts of silicon dioxide modified melamine cyanurate;
0.5-5 parts of epoxy polysiloxane;
0.1-1 part of antioxidant;
0.1-1 part of lubricant;
the polyamide is one or two of PA6 and PA 66.
The invention has the innovation points that silicon dioxide is introduced on the surface of the flame retardant MCA, the migration of the flame retardant MCA (melamine cyanurate) is limited by the silicon dioxide, and meanwhile, the inorganic silicon component with a porous structure is introduced, so that the heat resistance of the material is improved, the generation of molten drops in the combustion process of polyamide is reduced, and the flame retardant property of the material is improved. Moreover, the epoxy polysiloxane is adopted as the epoxy polysiloxane to improve the compatibility of the flame retardant (silicon dioxide modified melamine cyanurate) and the polyamide resin, and further reduce the migration of the flame retardant. Meanwhile, a siloxane layer is enriched on the surface of the flame retardant (silicon dioxide modified melamine cyanurate) through the reaction of the epoxy group and the surface amino group of the flame retardant (silicon dioxide modified melamine cyanurate), so that the toughness of the material is improved, and the toughness reduction caused by the addition of the flame retardant is compensated. The material has excellent mechanical properties, does not bloom for a long time in a high-temperature and high-humidity environment, and is suitable for the field of precise electric circuits.
Further preferably, the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material is composed of the following materials in parts by weight:
630-50 parts of PA;
PA 6630-50 shares;
12-20 parts of silicon dioxide modified melamine cyanurate;
1-3 parts of epoxy polysiloxane;
0.2-0.5 part of antioxidant;
0.3-0.8 part of lubricant.
Still more preferably, the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material is composed of the following materials in parts by weight:
640-50 parts of PA;
PA 6640-45 shares;
12-15 parts of silicon dioxide modified melamine cyanurate;
1-3 parts of epoxy polysiloxane;
0.2-0.5 part of antioxidant;
0.3-0.8 part of lubricant.
The preparation of the silicon dioxide modified melamine cyanurate comprises the following steps:
(1) dissolving cetyl trimethyl ammonium bromide in a mixed solution of ethyl ether and ethanol, adding melamine isocyanate, performing ultrasonic dispersion, then adding an ammonia water solution, and mechanically stirring to obtain a mixture;
(2) adding ethyl orthosilicate into the mixture obtained in the step (1), stirring, adding gamma-aminopropyltriethoxysilane, continuing stirring to obtain a white solid, filtering, washing with water, washing with ethanol, and drying to obtain the porous silicon dioxide coated melamine cyanurate.
In the step (1), the dosage ratio of the hexadecyl trimethyl ammonium bromide to the diethyl ether to the ethanol to the melamine isocyanate to the ammonia water solution is 50 g: 1000 mL-3000 mL: 2000 mL-4000 mL: 400 g-600 g: 4000g to 6000g, more preferably 50 g: 1500 mL-2500 mL: 2500 mL-3500 mL: 450 g-550 g: 4500 g-5500 g, more preferably 50 g: 2000mL of: 3000 mL: 500 g: 5000 g.
Ultrasonic dispersion is carried out for 5-15min,
the pH value of the ammonia water solution is 9-10.
The mechanical stirring conditions are as follows: mechanically stirring for 0.2-1 h at 20-30 ℃; more preferably, the mechanical stirring is carried out at 25 ℃ for 0.5 h.
In the step (2), the ratio of the ethyl orthosilicate, the gamma-aminopropyltriethoxysilane to the hexadecyl trimethyl ammonium bromide in the step (1) is 200-300 g: 30 g-70 g: 30g to 70g, more preferably 240g to 260 g: 40 g-60 g: 40 g-60 g, most preferably 250 g: 50 g: 50 g.
And adding tetraethoxysilane, stirring for 2-6 h, further preferably adding tetraethoxysilane, stirring for 3-5 h, most preferably adding tetraethoxysilane, and stirring for 4 h.
And (3) adding the gamma-aminopropyltriethoxysilane, then continuing to stir for 2-6 h, further preferably adding the gamma-aminopropyltriethoxysilane, then continuing to stir for 3-5 h, and most preferably adding the gamma-aminopropyltriethoxysilane, then continuing to stir for 4 h.
The drying conditions are as follows: drying at 70-90 deg.C for 18-30 h, preferably at 75-85 deg.C for 22-26 h, and most preferably at 80 deg.C for 24h
The epoxy polysiloxane is a compound of terminal epoxy polysiloxane and lateral epoxy polysiloxane, the weight ratio of the terminal epoxy polysiloxane to the lateral epoxy polysiloxane is 3:1-1:1, and the viscosity of the polysiloxane is 500-2000mm2(ii) an epoxy value of 0.6 to 0.9.
The antioxidant is one or two of 1098 and 168.
The lubricant is one or more than two (including two) of ethylene bis-stearic acid amide, modified ethylene bis-fatty acid amide (TAF), stearate and polyethylene wax.
The preparation method of the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material comprises the following steps:
feeding polyamide, silicon dioxide modified melamine cyanurate, epoxy polysiloxane, an antioxidant and a lubricant from a main feeding port of a double-screw extruder, fully melting and plasticizing the materials under the actions of double-screw conveying and shearing, and then bracing, cooling and granulating to obtain the soaking precipitation-resistant halogen-free flame-retardant reinforced polyamide composite material.
The temperature of melting and plasticizing in the double-screw extruder is 220-265 ℃, and the rotation speed of the screw is 400-600 rpm/min.
Compared with the prior art, the invention has the following advantages:
(1) a porous silica protective layer is introduced to modify the surface of the MCA flame retardant, so that the MCA flame retardant is protected and blocked, and the migration of the MCA flame retardant under the action of high temperature and high humidity is reduced;
(2) the MCA flame-retardant system introduces an organic silicon component, and the flame-retardant efficiency of the material is improved through the nitrogen-silicon flame-retardant synergistic effect, so that the material does not generate molten drops during combustion, and the UL 94V-0 requirement is met;
(3) siloxane long chains are introduced on the surfaces of the flame retardant rigid particles through chemical reaction in the extrusion process, so that the compatibility of the flame retardant and polyamide is improved, and the toughness of the material is improved.
(4) The soaking precipitation-resistant halogen-free flame-retardant polyamide material prepared by the invention has the advantages of high flame-retardant efficiency, good toughness, soaking precipitation resistance, simple and convenient processing and the like, and is widely applied to the field of electronics and electricity.
Detailed Description
The invention will now be further illustrated by reference to the following examples:
polyamide 66 (warpeak, 1106), polyamide 6 (new drawing, 2500), lubricant TAF (santai gloss), silica modified melamine cyanurate (homemade), epoxy polysiloxane (dow corning, DC 345), melamine cyanurate (basf), 1098 (commercially available).
Examples 1 to 3 and comparative examples 1 to 2
The preparation of the silicon dioxide modified melamine cyanurate comprises the following steps:
(1) 50g of cetyltrimethylammonium bromide are dissolved in 2000mL of diethyl ether and 3000mL of ethanol, 500g of melamine isocyanate are added and the mixture is subjected to ultrasonic dispersion for 10 min. Subsequently, 5000g of an aqueous ammonia solution having a pH of 9.5 was added thereto, and the mixture was mechanically stirred at room temperature and 25 ℃ for 0.5h to obtain a mixture.
(2) Adding 250g of ethyl orthosilicate into the mixture, stirring for 4h, then slowly adding 50g of gamma-aminopropyltriethoxysilane, continuing stirring for 4h, filtering the obtained white solid, washing with water and ethanol, and drying at 80 ℃ for 24h to obtain the silicon dioxide modified melamine cyanurate.
Silica modified melamine cyanurate
Feeding polyamide 66, polyamide 6, silicon dioxide modified melamine cyanurate, epoxy polysiloxane, an antioxidant 1098 and a lubricant TAF from a main feeding port of a double-screw extruder, fully melting and plasticizing the materials under the actions of double-screw conveying and shearing, bracing, cooling and granulating to obtain the precipitation-resistant halogen-free flame-retardant polyamide composite material, wherein the melting and plasticizing temperature in the double-screw extruder is 235-255 ℃, and the rotation speed of a screw is 500 rpm/min.
The material proportions of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
| Raw materials | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| PA66 | 45 | 45 | 45 | 45 | 45 |
| PA6 | 40 | 41 | 42 | 40 | 40 |
| Silica modified MCA | 14 | 13 | 12 | / | 14 |
| MCA | / | / | / | 14 | / |
| Antioxidant 1098 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Epoxy polysiloxane | 1 | 1.5 | 2 | 0 | 0 |
| TAF | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The pellets were injection molded into corresponding test specimens according to ISO test standards and then tested after being left for 24 hours at 23. + -. 2 ℃ under a relative humidity of 50. + -. 5%. Flame retardant precipitation resistance test the flame retardant content in water was determined after 24h boiling water treatment of the material, and the results obtained by the test are shown in table 2.
TABLE 2
| Item | Unit of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Tensile strength | MPa | 65 | 62 | 60 | 60 | 66 |
| Bending strength | MPa | 115 | 113 | 110 | 104 | 119 |
| Charpy unnotched impact | kJ/m2 | 98 | 100 | 105 | 50 | 70 |
| Vertical combustion UL94 | Class | V-0 | V-0 | V-0 | V-2 | V-0 |
| Content of flame retardant | ppm | 150 | 150 | 150 | 1000 | 250 |
The polyamide materials obtained in the embodiments 1 to 3 have excellent flame retardant property and toughness and low migration rate of the flame retardant, and are suitable for the fields of precise electronic materials, textile electrical appliances and the like.
Comparative examples 1 to 2
Comparative example 1 did not employ modified MCA and epoxy polysiloxane and comparative example 2 did not employ epoxy polysiloxane.
In the embodiments 1-3, the modified MCA and the epoxy polysiloxane are compounded, so that the flame retardant efficiency of the system is greatly improved, the flame retardant performance is improved, and the toughness of the material is kept, so that the flame retardant material is applicable to the field of precise electronic circuits. The silicon dioxide modified melamine cyanurate introduces silicon dioxide on the surface of the flame retardant MCA, the migration of the flame retardant MCA (melamine cyanurate) is limited by the silicon dioxide, and meanwhile, the inorganic silicon component with a porous structure is introduced, so that the heat resistance of the material is improved, the generation of molten drops in the combustion process of polyamide is reduced, and the flame retardant performance of the material is improved.
The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the present invention.
Claims (6)
1. The preparation method of the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material is characterized in that the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material is prepared from the following materials in parts by weight:
65-90 parts of polyamide;
8-25 parts of silicon dioxide modified melamine cyanurate;
0.5-5 parts of epoxy polysiloxane;
0.1-1 part of antioxidant;
0.1-1 part of lubricant;
the polyamide is one or two of PA6 and PA 66;
the preparation method comprises the following steps:
feeding polyamide, silicon dioxide modified melamine cyanurate, epoxy polysiloxane, an antioxidant and a lubricant from a main feeding port of a double-screw extruder, fully melting and plasticizing the materials under the actions of double-screw conveying and shearing, and then bracing, cooling and dicing to obtain the soaking precipitation-resistant halogen-free flame-retardant polyamide composite material;
the preparation of the silicon dioxide modified melamine cyanurate comprises the following steps:
(1) dissolving cetyl trimethyl ammonium bromide in a mixed solution of ethyl ether and ethanol, adding melamine isocyanate, performing ultrasonic dispersion, then adding an ammonia water solution, and mechanically stirring to obtain a mixture;
the dosage ratio of the hexadecyl trimethyl ammonium bromide, the ethyl ether, the ethanol, the melamine isocyanate and the ammonia water solution is 50 g: 1000 mL-3000 mL: 2000 mL-4000 mL: 400 g-600 g: 4000 g-6000 g;
(2) adding ethyl orthosilicate into the mixture obtained in the step (1), stirring, adding gamma-aminopropyltriethoxysilane, continuing stirring to obtain a white solid, filtering, washing with water, washing with ethanol, and drying to obtain silicon dioxide modified melamine cyanurate;
the ratio of the ethyl orthosilicate, the gamma-aminopropyltriethoxysilane to the hexadecyl trimethyl ammonium bromide in the step (1) is 200-300 g: 30 g-70 g: 30g to 70 g.
2. The preparation method according to claim 1, characterized by comprising the following materials in parts by weight:
630-50 parts of PA;
PA 6630-50 shares;
12-20 parts of silicon dioxide modified melamine cyanurate;
1-3 parts of epoxy polysiloxane;
0.2-0.5 part of antioxidant;
0.3-0.8 part of lubricant;
the total weight of the PA6 and the PA66 is 65-90 parts.
3. The preparation method according to claim 1, characterized by comprising the following materials in parts by weight:
640-50 parts of PA;
PA 6640-45 shares;
12-15 parts of silicon dioxide modified melamine cyanurate;
1-3 parts of epoxy polysiloxane;
0.2-0.5 part of antioxidant;
0.3-0.8 part of lubricant;
the total weight of the PA6 and the PA66 is 65-90 parts.
4. The preparation method according to claim 1, wherein in the step (1), ultrasonic dispersion is performed for 5-15 min;
the pH value of the ammonia water solution is 9-10;
the mechanical stirring conditions are as follows: mechanically stirring for 0.2-1 h at 20-30 ℃.
5. The preparation method according to claim 1, wherein in the step (2), the tetraethoxysilane is added and stirred for 2-6 h;
adding gamma-aminopropyltriethoxysilane, and then continuing stirring for 2-6 h;
the drying conditions are as follows: drying for 18-30 h at 70-90 ℃.
6. The preparation method of claim 1, wherein the temperature for melt plasticizing in the twin-screw extruder is 220 ℃ to 265 ℃, and the number of screw revolutions is 400rpm to 600 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910033554.4A CN109735103B (en) | 2019-01-14 | 2019-01-14 | Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910033554.4A CN109735103B (en) | 2019-01-14 | 2019-01-14 | Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109735103A CN109735103A (en) | 2019-05-10 |
| CN109735103B true CN109735103B (en) | 2021-12-21 |
Family
ID=66364772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910033554.4A Active CN109735103B (en) | 2019-01-14 | 2019-01-14 | Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109735103B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980183A (en) * | 2019-12-18 | 2021-06-18 | 南京聚隆科技股份有限公司 | Precipitation-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof |
| CN112646365B (en) * | 2020-12-19 | 2022-03-29 | 杭州本松新材料技术股份有限公司 | Heat-conducting and flame-retardant polyamide composition for low-voltage electrical appliance and application thereof |
| CN114395124A (en) * | 2022-02-17 | 2022-04-26 | 江西中塑新材料科技有限公司 | Polyamide composite material and synthetic method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617861A (en) * | 2012-04-13 | 2012-08-01 | 浙江华亿工程设计有限公司 | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof |
| CN102964822A (en) * | 2012-12-12 | 2013-03-13 | 江苏天辰硅材料有限公司 | Silicon rubber toughened and modified nylon resin and preparation method thereof |
| CN103073715A (en) * | 2013-01-17 | 2013-05-01 | 湖南工业大学 | Preparation method of composite material for inorganic modified melamine chlorinated isocyanurate flame-retardant nylon 6 |
| CN103131164A (en) * | 2011-11-24 | 2013-06-05 | 深圳市兆威机电有限公司 | Additive for injection molding white polyamide (PA) plastic and method for injection molding white polyamide (PA) plastic piece |
| CN105670282A (en) * | 2016-04-05 | 2016-06-15 | 南京利华工程塑料有限公司 | High-flame-retardancy halogen-free non-reinforced polyamide (PA) material and preparation method thereof |
| CN106244172A (en) * | 2016-07-12 | 2016-12-21 | 伊科纳诺（北京）科技发展有限公司 | A kind of preparation method of the fire-retardant aerosil of Halogen synergistic |
| CN106832151A (en) * | 2017-01-13 | 2017-06-13 | 浙江泰普森休闲用品有限公司 | A kind of dissaving polymer with POSS as core and its preparation method and application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62109849A (en) * | 1985-11-06 | 1987-05-21 | Showa Denko Kk | Flame-retardant resin composition |
| DE602007004100D1 (en) * | 2007-07-04 | 2010-02-11 | Abb Research Ltd | High temperature vulcanized silicone rubber |
| US20100124663A1 (en) * | 2008-11-20 | 2010-05-20 | Alpha Technical Research Co. Ltd. | Resin composition and sheet using resin composition |
| CN106751788A (en) * | 2016-11-16 | 2017-05-31 | 马鞍山市华能电力线路器材有限责任公司 | A kind of thermal diffusivity good electric armour clamp fire-retardant nylon composite and preparation method thereof |
| CN108276766B (en) * | 2018-01-31 | 2020-10-30 | 宁波市汇博材料科技有限公司 | Flame-retardant nylon material and preparation method thereof |
| CN108424547B (en) * | 2018-02-14 | 2020-01-10 | 东华大学 | Hybrid modified melamine salt, preparation method and application thereof |
-
2019
- 2019-01-14 CN CN201910033554.4A patent/CN109735103B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131164A (en) * | 2011-11-24 | 2013-06-05 | 深圳市兆威机电有限公司 | Additive for injection molding white polyamide (PA) plastic and method for injection molding white polyamide (PA) plastic piece |
| CN102617861A (en) * | 2012-04-13 | 2012-08-01 | 浙江华亿工程设计有限公司 | Melamine cyanurate flame retardant agent containing organic silicone and preparation process thereof |
| CN102964822A (en) * | 2012-12-12 | 2013-03-13 | 江苏天辰硅材料有限公司 | Silicon rubber toughened and modified nylon resin and preparation method thereof |
| CN103073715A (en) * | 2013-01-17 | 2013-05-01 | 湖南工业大学 | Preparation method of composite material for inorganic modified melamine chlorinated isocyanurate flame-retardant nylon 6 |
| CN105670282A (en) * | 2016-04-05 | 2016-06-15 | 南京利华工程塑料有限公司 | High-flame-retardancy halogen-free non-reinforced polyamide (PA) material and preparation method thereof |
| CN106244172A (en) * | 2016-07-12 | 2016-12-21 | 伊科纳诺（北京）科技发展有限公司 | A kind of preparation method of the fire-retardant aerosil of Halogen synergistic |
| CN106832151A (en) * | 2017-01-13 | 2017-06-13 | 浙江泰普森休闲用品有限公司 | A kind of dissaving polymer with POSS as core and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 尼龙6/SiO2改性MCA复合材料的阻燃性能;魏珊珊;《材料研究学报》;20121231;第26卷(第6期);第627-631页 * |
| 己内酰胺与环硅氧烷阴离子开环共聚合的研究;冯建荣等;《高分子学报》;19900430(第2期);第193-198页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109735103A (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109735103B (en) | Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof | |
| KR101792338B1 (en) | Thermoplastic resin composition and molded parts using the same | |
| CN109438976B (en) | Copolymerized nylon product and preparation method thereof | |
| TWI644977B (en) | Thermoplastic resin composition and molded article formed by molding the same | |
| KR20010052161A (en) | Flame-proofed polyamide composition | |
| CN112795183B (en) | High-strength, low-shrinkage and low-precipitation environment-friendly flame-retardant polyamide composition and preparation method thereof | |
| EP3008111B1 (en) | Method for the preparation of aliphatic or partially aromatic polyamides comprising a solid state polymerisation | |
| CN100549095C (en) | Polyamide resin of a kind of halogen-free phosphor-free environmental protection inflaming retarding and preparation method thereof | |
| CN105419253A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN111484739A (en) | Flame-retardant reinforced polyamide composition and preparation method thereof | |
| EP3327062B1 (en) | Partially aromatic copolyamides with a high glass transition temperature and high degree of crystallinity | |
| CN110903644A (en) | Bio-based PA56T and PA56 composite material and preparation method thereof | |
| CN114292517A (en) | Flame-retardant polyamide composite material and preparation method and application thereof | |
| TWI631179B (en) | Polyamine resin composition and method for improving heat aging resistance of polyamine resin | |
| CN112322020B (en) | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof | |
| CN104072981A (en) | Halogen-free flame retardant polyamide material and preparation method thereof | |
| CN110885545B (en) | Weather-resistant flame-retardant PC/PBT alloy and preparation method thereof | |
| CN111225942B (en) | Improved polyamide stabilizers | |
| JP2005248032A (en) | Flame retardant aliphatic polyester resin composition | |
| EP2949693B1 (en) | A thermoplastic resin composition for automobiles and a molded product produced from the same | |
| EP4328455A2 (en) | Industrial fan or blower comprising a flame-retardant polyamide composition | |
| CN102051041B (en) | Engineering plastic raw material, engineering plastic and engineering plastic preparation method | |
| CN106398200A (en) | Water proof flame retardant polyamide material and preparation method thereof | |
| CN112724401B (en) | Polyamide composition and preparation method thereof | |
| DE60005006T2 (en) | FLAME-RETARDANT POLYAMIDE COMPOSITION |
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 |