CN109836813B - Nylon 6 composite material and preparation method thereof - Google Patents
Nylon 6 composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109836813B CN109836813B CN201910025722.5A CN201910025722A CN109836813B CN 109836813 B CN109836813 B CN 109836813B CN 201910025722 A CN201910025722 A CN 201910025722A CN 109836813 B CN109836813 B CN 109836813B
- Authority
- CN
- China
- Prior art keywords
- nylon
- nano
- parts
- silane
- modified
- 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
Abstract
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: nylon 680-120 parts, modified nano SiO215-30 parts of antioxidant, 0.3-1 part of toughening agent and 5-10 parts of flame retardant. The invention is prepared by mixing nano SiO2Modified and compounded with nylon 6, so that the nano SiO is ensured on the premise of improving the mechanical property of the nylon 6 material2Has good compatibility with nylon 6 and has good mixing effect with other components. Nylon 6 and nano SiO in a certain proportion2The obtained nylon 6 composite material has excellent mechanical property and flame retardant property, and is particularly suitable for manufacturing devices such as sockets and the like.
Description
Technical Field
The invention relates to a modification technology of a high polymer composition, in particular to a nylon 6 modified material and a preparation method thereof.
Background
The material requirements of the switch socket are as follows: it is required to have high strength, high toughness, high heat resistance, high flame retardancy, high electrical insulation properties, and the like. The conventional material selection in the industry is to use flame retardant PC (polycarbonate) materials. With the cost of the product being controlled, the use of polycaprolactam, commonly known as nylon 6(PA6), in electrical outlets has become a trend.
The flame retardant is added to improve the flame retardant performance of the material, but the flame retardant performance stability is poor due to uneven distribution of the flame retardant in the nylon 6. Meanwhile, in order to ensure the dimensional accuracy of the switch socket injection molding and keep the material to have certain rigidity, the nylon 6 is usually reinforced and modified by using glass fibers, but the glass fibers are modified, so that the material damages a device screw and a mold in the production process, floating fibers are easily generated on the surface of the injection molding due to the addition of the glass fibers, and the mechanical property of the material is reduced due to the addition of the glass fibers due to the poor compatibility of the glass fibers and nylon 6 resin. Chinese patent CN201410314292.6 discloses a high-performance flame-retardant PA6 alloy and a preparation method thereof, the preparation raw materials comprise PA 670-90 parts, treated basic magnesium sulfate whisker 10-16 parts, nano-silica 1-5 parts and antioxidant 0.2-0.5 part, the treated basic magnesium sulfate whisker is prepared by the following steps of dissolving 1-5g of coupling agent in 100m1 ethanol solution, then placing 30-60g of basic magnesium sulfate, performing ultrasonic dispersion, filtering and drying for later use, wherein the coupling agent is titanate coupling agent AC-201; in the patent, basic magnesium sulfate is used as a flame retardant to improve the flame retardant property of PA6 and improve the mechanical property of PA6 alloy, but the flame retardant is used in a large amount and has high cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nylon composite material with good flame retardant property and mechanical property, which is particularly suitable for being used as a raw material for preparing plastic parts arranged in sockets and converters.
The technical scheme of the invention is to provide a nylon 6 composite material, which comprises the following components in parts by weight: nylon 680-120 parts, modified nano SiO215-30 parts of antioxidant, 0.3-1 part of toughening agent and 5-10 parts of flame retardant.
Further, modified nano SiO2The particle size of (B) is 100-400 nm.
Further, modified nano SiO2Is nano SiO2Obtained by grafting modification of adipic acid.
Further, modified nano SiO2The modification process comprises the reaction of adipic acid and thionyl bromide to complete acyl bromination of the adipic acid, and the adipic acid after acyl bromination is reacted with nano SiO2The hydroxyl on the surface reacts to obtain the adipic acid grafted and modified nano SiO2。
Further, the antioxidant is a mixture of 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and 626 (bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite) in a mass ratio of 2-3: 1.
Further, the toughening agent is a high polymer of ethylene and octene.
Further, the flame retardant is silane-impregnated nano Mg (OH)2silane-Nano Mg (OH)2The particle size is 80-200 nm.
Further, the silane used for wetting the flame retardant is one or more of YDH-151 (vinyl triethoxysilane), KH550 (gamma-aminopropyltriethoxysilane), KH602 (N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane).
Further, nano Mg (OH)2The infiltration process comprises the following steps: mixing silane, isopropanol and water according to the mass ratio of 1-3: 5-8: 1 to prepare a modified solution for later use; nano Mg (OH)2Stirring at 500-800r/min while spraying the modified solution to Mg (OH)2The surface is infiltrated, and the infiltrated Mg (OH)2Baking for 10-15min at the temperature of 100-130 ℃ to obtain silane-nano Mg (OH) infiltrated by silane2。
The invention also provides a preparation method of the nylon 6 composite material, which comprises the following steps:
(1) mixing the raw materials according to a ratio, and feeding the mixture into a double-screw extruder;
(2) the heating section of the double-screw extruder is nine sections, the processing temperature of each section is 230-245 ℃ from one section to six sections, and the processing temperature of the seventh section to the ninth section is 250-260 ℃;
(3) extruding and granulating to obtain the nylon 6 composite material.
The invention has the advantages and beneficial effects that: the invention is prepared by mixing nano SiO2Modified and compounded with nylon 6, so that the nano SiO is ensured on the premise of improving the mechanical property of the nylon 6 material2Has good compatibility with nylon 6 and has good mixing effect with other components. Nylon 6 and nano SiO in a certain proportion2The obtained nylon 6 composite material has excellent mechanical property and flame retardant property, and is particularly suitable for manufacturing devices such as sockets and the like.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Nano SiO2Can be used as an inorganic filling aid to improve the strength of the material, but the nano SiO2When the modified nano SiO is added into nylon 6, the dispersibility is poor, the compatibility with matrix nylon 6 is poor, and the strength of the nylon 6 material can be reduced2Added into a nylon 6 matrix, and the compatibility of an inorganic phase and an organic phase is improved. Modified nano SiO2The modification principle of (A) is shown in the following reaction formula:
firstly, adipic acid reacts with thionyl bromide to complete acyl bromination of adipic acid, and the adipic acid after acyl bromination is reacted with nano SiO2The hydroxyl on the surface reacts to obtain the adipic acid grafted and modified nano SiO2. The modified nano SiO2Solves the problem of inorganic SiO2The micromolecules are easy to agglomerate and are distributed unevenly, and bromine is introduced to ensure that the modified nano SiO2Besides the reinforcing function, the flame retardant property of the material can be improved.
In particular, the principle of enhancement: nano SiO2Uniformly dispersed in nylon 6 resin, and when the material injection molding product is subjected to external force, the force is in SiO2And the net-shaped structure formed by the nylon 6 resin high molecular chain is uniformly dispersed, so that the failure risks of cracking and the like of the material are reduced. The flame retardant principle is as follows: nano SiO2The adipic acid which is subjected to acyl bromination is grafted and modified, so that the nylon 6 resin can generate free radical Br and free radical HO with strong activity when being heated and subjected to decomposition reaction when meeting open fire, the free radical Br reacts with the nylon 6 resin to generate hydrogen bromide (HBr), and the HBr reacts with the free radical HO with strong activity to obtain H2O and Br, in which stage Br is regenerated, the strong active radical HO is suppressed, the concentration is reduced, and the combustion chain reaction is suppressed.
Nano Mg (OH)2The inorganic filler can be used as a flame retardant, but when added to nylon 6, the inorganic filler has poor compatibility with the organic phase, resulting in Mg (OH)2The problem of non-uniform dispersion in the nylon 6 matrix, therefore, in the present invention, Mg (OH)2Modification by silane impregnation to give Mg (OH)2The bonding ability with nylon 6 is enhanced, and the compatibility is improved. Mg (OH)2The flame retardant mechanism of (a) is: mg (OH)2Decomposition to H by heating2O and MgO, the decomposition process absorbs a large amount of heat, and H2O can reduce the oxygen concentration, and MgO can be attached to the surface of the resin, and all the aspects are mutually matched to prevent combustion. The flame retardant mechanism and the modified nano SiO2The flame retardant mechanism (2) can play a role in synergistic flame retardance.
Nano Mg (OH)2The process of modification by silane impregnation is as follows: taking a solution prepared from silane, isopropanol and water according to a mass ratio of 2:7:1 as a modified solution for later use; when nano Mg (OH)2Spraying the modified solution to Mg (OH) in a spraying mode when stirring at a high speed in a stirring device with the rotating speed of 500-800r/min2The surface is infiltrated, and the infiltrated Mg (OH)2Baking at 110 deg.C for 10-15min to obtain silane-nanometer Mg (OH) impregnated with silane2。
In the preparation process, through processing of processing sections at different temperatures, the components of the nylon 6 composite material are well fused with each other, the components are uniformly dispersed in a matrix, and the material has good strength, toughness, flame retardant property and the like.
The nylon 6 composite material obtained by the invention has the advantages of low linear expansion coefficient, low die damage, excellent appearance, high strength, high flame retardant property and the like, and can be widely applied to the fields of switch sockets and the like.
The present invention will be described more specifically with reference to preferred examples wherein the antioxidant is a mixture of 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and 626 (bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite) in a mass ratio of 2-3: 1; the toughening agent is POE (high polymer of ethylene and octene); the melt index of the nylon 6 is 14-40g/10 min.
Example 1
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO215 parts, 0.5 part of antioxidant, 10 parts of toughening agent and silane-nano Mg (OH)25 parts of the raw materials. Wherein, the modified nano SiO2The particle diameter of 100-150nm, silane-nano Mg (OH)2The particle size is 80-100 nm.
The preparation method comprises the following steps: mixing the raw materials, and feeding the mixture into a double-screw extruder, wherein the length-diameter ratio of a screw of the extruder is 37-45, and the processing parameters are as follows:
example 2
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO218 portions, 0.5 portion of antioxidant, 11 portions of toughening agent and silane-nano Mg (OH)26 parts. Wherein, the modified nano SiO2Has a particle diameter of 150-200nm, silane-nano Mg (OH)2The particle size is 100-120 nm.
The preparation method is the same as example 1.
Example 3
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO221 parts, antioxidant 0.5 part, toughening agent 12 parts, silane-nano Mg (OH)27 parts. Wherein, the modified nano SiO2Has a particle size of 200-250nm, silane-nano Mg (OH)2The particle size is 120-140 nm.
The preparation method is the same as example 1.
Example 4
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO224 parts, 0.5 part of antioxidant, 13 parts of toughening agent and silane-nano Mg (OH)28 parts. Wherein, the modified nano SiO2The particle size of 250-300nm, silane-nano Mg (OH)2The particle size is 140-160 nm.
The preparation method is the same as example 1.
Example 5
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO227 parts of antioxidant, 0.5 part of toughener, 14 parts of silane-nano Mg (OH)29 parts. Wherein, the modified nano SiO2The particle diameter of 300-350nm, silane-nano Mg (OH)2The particle size is 160-180 nm.
The preparation method is the same as example 1.
Example 6
The invention provides a nylon 6 composite material which comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO230 parts of antioxidant, 0.5 part of flexibilizer, 15 parts of silane-nano Mg (OH)210 parts. Wherein, the modified nano SiO2Has a particle diameter of 350-400nm, silane-nano Mg (OH)2The particle size is 180-200 nm.
The preparation method is the same as example 1.
Comparative example 1
By using unmodified nano SiO2The paint comprises the following components in parts by weight: 6100 portions of nylon, nano SiO224 parts, 0.5 part of antioxidant, 13 parts of toughening agent and silane-nano Mg (OH)28 parts. Wherein, the nano SiO2The particle size of 250-300nm, silane-nano Mg (OH)2The particle size is 140-160 nm.
The preparation method is the same as example 1.
Comparative example 2
Using unmodified nano Mg (OH)2The paint comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO224 parts, 0.5 part of antioxidant, 13 parts of toughening agent and nano Mg (OH)28 parts. Wherein, the nano SiO2The particle size of 250-300nm, silane-nano Mg (OH)2The particle size is 140-160 nm.
The preparation method is the same as example 1.
Comparative example 3
Changing modified nano SiO2And change toSex Mg (OH)2The particle size of the composite material comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO224 parts, 0.5 part of antioxidant, 13 parts of toughening agent and silane-nano Mg (OH)28 parts. Wherein, the nano SiO2Has a particle diameter of 50-100nm, and silane-nano Mg (OH)2The particle size is 60-80 nm.
The preparation method is the same as example 1.
Comparative example 4
Changing modified nano SiO2And modified Mg (OH)2The particle size of the composite material comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO224 parts, 0.5 part of antioxidant, 13 parts of toughening agent and silane-nano Mg (OH)28 parts. Wherein, the nano SiO2The particle diameter of 400-450nm, silane-nano Mg (OH)2The particle size is 200-220 nm.
The preparation method is the same as example 1.
Comparative example 5
Reduction of modified nano SiO2And modified Mg (OH)2The formula comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO212 parts of antioxidant 0.5 part, toughening agent 13 parts and silane-nano Mg (OH)24 parts. Wherein, the nano SiO2The particle size of 250-300nm, silane-nano Mg (OH)2The particle size is 140-160 nm.
The preparation method is the same as example 1.
Comparative example 6
Adding modified nano SiO2And modified Mg (OH)2The formula comprises the following components in parts by weight: 6100 portions of nylon, modified nano SiO235 parts, 0.5 part of antioxidant, 13 parts of flexibilizer and silane-nano Mg (OH)212 parts. Wherein, the nano SiO2The particle size of 250-300nm, silane-nano Mg (OH)2The particle size is 140-160 nm.
The preparation method is the same as example 1.
The materials prepared in the above examples and comparative examples were injection molded into samples and tested according to the following criteria, with the following results:
comparative example 1 of the invention Nano SiO2The material is not subjected to grafting modification, has poor bonding property with PA6 material, and is easy to generate nano SiO2Agglomerated and thus passed through the nano SiO2The modified PA6 material has low mechanical properties, large linear expansion coefficient and poor injection molding appearance. In addition, SiO is used as the material2Br element is introduced without grafting modification, and the modified PA6 has poor flame retardant property which can only reach UL94 HB.
Comparative example 2 nanometer Mg (OH)2The modified PA6 material has the advantages that the modified PA6 material is not soaked by silane, the bonding property with the PA6 material is poor, the tensile strength, the bending modulus and the injection molding appearance are good, but the notch impact strength of the material is low; and due to unmodified nano Mg (OH)2The agglomeration is easy to occur, the flame retardant property of the modified PA6 is influenced, and the flame retardant grade is UL94V 1.
Comparative example 3 modified Nano SiO2And silane-nano Mg (OH)2The particle size is smaller, the agglomeration effect is increased, and the two nano materials are easy to agglomerate, so that the mechanical property, the flame retardant grade, the injection molding appearance and the like of the material are poorer. Comparative example 4 modified Nano SiO2And silane-nano Mg (OH)2The particle size is larger, the bonding property with PA6 is poor although the particle size is grafted and infiltrated, the notch impact strength of the material is lower, and the injection molding appearance is poor.
Comparative example 5 modified Nano SiO2And silane-nano Mg (OH)2The addition amount is small, the bending modulus of the material is low, the linear expansion coefficient is large, the rigidity of the modified PA6 is poor, the injection shrinkage rate of the material is large, and the dimensional stability is poor. Comparative example 6 modified Nano SiO2And silane-nano Mg (OH)2The addition amount is more, the bending modulus of the material is high, the linear expansion coefficient is small, the rigidity of the material is good, the injection molding size stability is good, the distribution of PA6 high molecular chains is damaged due to the addition amount, the notch impact strength of the material is lower, and the injection molding appearance is poorer.
Examples 1-6, modified NanoSiO2And silane-nano Mg (OH)2The particle size range of the material is preferred, the addition weight portion is preferred, and the material is grafted with acyl-brominated adipic acid and silane-infiltrated nano Mg (OH)2A flame-retardant composite system is formed, and the bromine is introduced to reduce the use amount of the flame retardant in the modification process while playing a role in enhancing, so that in examples 1-6, the addition weight part of the flame retardant is only 5-10 parts. Modified nano SiO2And silane-nano Mg (OH)2The modified PA6 material has the advantages of excellent mechanical property, excellent injection molding appearance, small linear expansion coefficient, excellent flame retardant property and the like, and in addition, when the material scheme is used for injection molding production, a mold only needs to be wiped in a fixed shift, so that the problem that the mold needs to be frequently polished in the traditional glass fiber reinforced material is solved, and the production efficiency is improved.
Materials, reagents and experimental equipment related to the embodiment of the invention are all commercial products in the field of high polymer materials unless specified otherwise.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (9)
1. The nylon 6 composite material is characterized by comprising the following components in parts by weight: 120 parts of nylon 680-one, 215-30 parts of modified nano SiO, 0.3-1 part of antioxidant, 10-15 parts of toughening agent and 5-10 parts of flame retardant, wherein the modified nano SiO2 is obtained by grafting and modifying nano SiO2 with adipic acid, and the flame retardant is silane-nano Mg (OH)2 soaked by silane.
2. The nylon 6 composite material of claim 1, wherein the modified nano-SiO 2 has a particle size of 100-400 nm.
3. The nylon 6 composite material of claim 1, wherein the modification process of the modified nano SiO2 is to react adipic acid with thionyl bromide to brominate the adipic acid, and then the acyl-brominated adipic acid reacts with hydroxyl on the surface of nano SiO2 to obtain the adipic acid graft-modified nano SiO 2.
4. The nylon 6 composite of claim 1, wherein the silane-nano mg (oh)2 particle size is 80-200 nm.
5. The nylon 6 composite material of claim 4, wherein the infiltration process of nano Mg (OH)2 is: mixing silane, isopropanol and water according to the mass ratio of 1-3: 5-8: 1 to prepare a modified solution for later use; stirring the nano Mg (OH)2 at the rotation speed of 500-800r/min, spraying the modified solution on the surface of the Mg (OH)2 for infiltration, and baking the infiltrated Mg (OH)2 at the temperature of 100-130 ℃ for 10-15min to obtain silane-nano Mg (OH)2 infiltrated by silane.
6. The nylon 6 composite of claim 4 or 5, wherein the silane is one or more of vinyltriethoxysilane, γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane.
7. The nylon 6 composite of claim 1, wherein the antioxidant is a mixture of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite in a mass ratio of 2-3: 1.
8. The nylon 6 composite of claim 1, wherein the toughening agent is a high polymer of ethylene and octene.
9. The process for the preparation of nylon 6 composite according to any of claims 1 to 8, characterized in that it comprises the following steps:
(1) mixing the raw materials according to a ratio, and feeding the mixture into a double-screw extruder;
(2) the heating section of the double-screw extruder is nine sections, the processing temperature of each section is 230-245 ℃ from one section to six sections, and the processing temperature of the seventh section to the ninth section is 250-260 ℃;
(3) extruding and granulating to obtain the nylon 6 composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910025722.5A CN109836813B (en) | 2019-01-11 | 2019-01-11 | Nylon 6 composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910025722.5A CN109836813B (en) | 2019-01-11 | 2019-01-11 | Nylon 6 composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109836813A CN109836813A (en) | 2019-06-04 |
| CN109836813B true CN109836813B (en) | 2021-09-03 |
Family
ID=66883778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910025722.5A Active CN109836813B (en) | 2019-01-11 | 2019-01-11 | Nylon 6 composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109836813B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114806150A (en) * | 2021-10-26 | 2022-07-29 | 安徽科高新材料有限公司 | Antistatic nylon and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423666A (en) * | 2008-10-31 | 2009-05-06 | 广东新会美达锦纶股分有限公司 | Halogen-free flame retardant polyamide 6 composition |
| EP2180018A1 (en) * | 2007-08-01 | 2010-04-28 | Kuraray Co., Ltd. | Polyamide composition |
| CN102337027A (en) * | 2010-07-23 | 2012-02-01 | 中国石油化工股份有限公司 | Special PA6 injection molding material used for direct injection molding and preparation method thereof |
| CN103044901A (en) * | 2012-12-17 | 2013-04-17 | 株洲时代新材料科技股份有限公司 | High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof |
| CN104151820A (en) * | 2014-08-19 | 2014-11-19 | 南通瑞隆新材料有限公司 | Preparation method of enhanced flame-retardant nylon PA66 modified engineering plastic |
| CN104804425A (en) * | 2015-05-20 | 2015-07-29 | 叶芳 | Novel polyamide nanocomposite and preparation method thereof |
| CN106675011A (en) * | 2016-11-30 | 2017-05-17 | 宁波仁慈新材料科技有限公司 | Cross-linkable radiation-resistant high-flame-retardant low-smoke zero-halogen PA (Polyamide) and preparation method thereof |
-
2019
- 2019-01-11 CN CN201910025722.5A patent/CN109836813B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2180018A1 (en) * | 2007-08-01 | 2010-04-28 | Kuraray Co., Ltd. | Polyamide composition |
| CN101423666A (en) * | 2008-10-31 | 2009-05-06 | 广东新会美达锦纶股分有限公司 | Halogen-free flame retardant polyamide 6 composition |
| CN102337027A (en) * | 2010-07-23 | 2012-02-01 | 中国石油化工股份有限公司 | Special PA6 injection molding material used for direct injection molding and preparation method thereof |
| CN103044901A (en) * | 2012-12-17 | 2013-04-17 | 株洲时代新材料科技股份有限公司 | High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof |
| CN104151820A (en) * | 2014-08-19 | 2014-11-19 | 南通瑞隆新材料有限公司 | Preparation method of enhanced flame-retardant nylon PA66 modified engineering plastic |
| CN104804425A (en) * | 2015-05-20 | 2015-07-29 | 叶芳 | Novel polyamide nanocomposite and preparation method thereof |
| CN106675011A (en) * | 2016-11-30 | 2017-05-17 | 宁波仁慈新材料科技有限公司 | Cross-linkable radiation-resistant high-flame-retardant low-smoke zero-halogen PA (Polyamide) and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "有机化纳米SiO2填充改性尼龙6复合材料的研究";杜拴丽等;《塑料工业》;20070831;第35卷(第8期);25-27 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109836813A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110804282B (en) | Modified flat glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof | |
| CN110698836B (en) | High-strength polycarbonate composite material for plastic-coated aluminum and preparation method thereof | |
| CN109265990A (en) | High glass fire-retarding reinforced polyamide composition | |
| CN110467804B (en) | Bio-based nylon composite PLA material and preparation method thereof | |
| CN103709659A (en) | Glass fiber reinforced PBT/PET alloy material | |
| CN111073245B (en) | Regenerated polycarbonate composite material and preparation method thereof | |
| CN105131430A (en) | Halogen-free flame-retardant long-glass-fiber reinforced polypropylene composite | |
| CN112625405B (en) | Low-smoke density halogen-free flame-retardant reinforced PBT/PET compound and preparation method and application thereof | |
| CN110256825A (en) | A kind of fiberglass reinforced fire retardant PET composite material and preparation method thereof | |
| CN109836813B (en) | Nylon 6 composite material and preparation method thereof | |
| CN108299803B (en) | High-flame-retardant transparent PET material and preparation method thereof | |
| CN104774440A (en) | High-fluidity fiber reinforced PC/ASA composite material and product thereof | |
| KR20170110817A (en) | Surface treatment method of halloysite nanotube | |
| CN111363318A (en) | Flame-retardant smoke-inhibiting PTT polyester composite material and preparation method therefor | |
| CN114806150A (en) | Antistatic nylon and preparation method thereof | |
| CN113265145A (en) | Carbon fiber reinforced polyphenylene sulfide composite material and preparation method thereof | |
| CN106751713A (en) | A kind of polyketone composite of flame retardant type fibre reinforced and preparation method thereof | |
| CN111154200A (en) | High-melt-strength PVC-U water supply pipe and preparation method thereof | |
| CN105111615A (en) | Energy-saving light-weight architectural wood-plastic decorating material | |
| CN110655714A (en) | Special polypropylene composite plastic for electric appliances and preparation method thereof | |
| CN104513486B (en) | Conductive thermoplastic resin composition | |
| KR20150076619A (en) | Polyamide Reinforced Resin Composition | |
| CN113897038B (en) | High-heat-resistance PBT composition, and preparation method and application thereof | |
| CN110283442B (en) | Low-VOC toughened porcelain white flame-retardant PC and preparation method thereof | |
| CN106566240A (en) | Antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting 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 |