CN114031793A - Polyamide composition and preparation method and application thereof - Google Patents

Polyamide composition and preparation method and application thereof Download PDF

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Publication number
CN114031793A
CN114031793A CN202111255009.3A CN202111255009A CN114031793A CN 114031793 A CN114031793 A CN 114031793A CN 202111255009 A CN202111255009 A CN 202111255009A CN 114031793 A CN114031793 A CN 114031793A
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cyclodextrin
parts
ion
ether
polyamide composition
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CN114031793B (en
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林洁龙
张超
张永
肖军华
刘纪庆
叶士兵
安朋
王飞
邱志强
付大炯
吴鹏
许建稳
夏建盟
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Jiangsu Kingfa New Material Co Ltd
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention discloses a polyamide composition, which comprises the following components in parts by weight: 100 parts of polyamide resin; 10-40 parts of a flame retardant; 0.01-10 parts of irradiation crosslinking agent; 0.1-2 parts of cyclodextrin or cyclodextrin derivative; 0.1-1.5 parts of metal salt; the polyamide composition has a cross-linking structure among polyamide molecules. According to the invention, a certain amount of cyclodextrin or cyclodextrin derivatives is added into the irradiation crosslinking polyamide resin system, so that the fluidity of the composition can be obviously improved, and the anti-creeping stability after multiple melting processing is ensured. Meanwhile, the metal salt improves the defects of thermal decomposition and precipitation of the cyclodextrin or the derivatives thereof.

Description

Polyamide composition and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyamide composition and a preparation method and application thereof.
Background
The irradiation crosslinking is a technical means for initiating crosslinking reaction between polymer long chains by using various radiations, and the irradiation source can be selected from electron beams, gamma rays, neutron beams, particle beams and the like according to the polymer category and performance requirements. For polyamide materials, typically radiation crosslinking agents that need to be used are triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), methyl triallyl isocyanurate (TMAIC). The polyamide resin composition after irradiation crosslinking can have good anti-creeping property. However, the irregular crosslinking phenomenon between the resin matrices of the crosslinked polyamide composition affects the leakage prevention property after melt processing.
The prior art generally improves melt flow by adding inorganic fillers. However, when applied to some light and thin parts with low density and strong flexibility, it is difficult to adopt the above method.
Disclosure of Invention
The invention aims to provide a polyamide composition which has good leak-proof electric stability and melt processability.
Another object of the present invention is to provide a process for producing the above polyamide composition.
The invention is realized by the following technical scheme:
the polyamide composition comprises the following components in parts by weight:
100 parts of polyamide resin;
10-40 parts of a flame retardant;
0.01-10 parts of irradiation crosslinking agent;
0.1-2 parts of cyclodextrin or cyclodextrin derivative;
0.05-1.5 parts of metal salt;
the polyamide composition has a cross-linking structure among polyamide molecules;
the flame retardant is a brominated flame retardant/flame retardant synergist compound system;
the metal ion of the metal salt is selected from at least one of lithium ion, sodium ion, potassium ion, calcium ion, zinc ion or copper ion, and the anion paired with the metal ion is selected from at least one of halogen ion, carbonate ion, nitrate ion, sulfate ion or acetate ion.
From the viewpoint of CTI stability and precipitation improvement, preferably, the content of the cyclodextrin or the derivative thereof is 0.2 to 0.9 part, and the content of the metal salt is 0.1 to 0.6; more preferably, the content of the cyclodextrin or the derivative thereof is 0.3 to 0.6 part, and the content of the metal salt is 0.15 to 0.4 part.
The irradiation crosslinking agent is selected from at least one of triallyl cyanurate, triallyl isocyanurate, methyl triallyl isocyanurate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate or dipropylene glycol diacrylate.
The cyclodextrin or the derivative thereof is at least one selected from beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl-beta-cyclodextrin, sulfobutyl ether-beta-cyclodextrin, disaccharide-beta-cyclodextrin, methyl-beta-cyclodextrin and hydroxyethyl-beta-cyclodextrin;
preferably, the cyclodextrin or its derivative is selected from beta-cyclodextrin. The preferred cyclodextrins are more resistant to leaching.
The brominated flame retardant is selected from brominated polystyrene, polybrominated styrene, brominated polyphenylene ether, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromobiphenyl, hexabromobiphenyl oxide, octabromobiphenyl oxide, decabromobiphenyl oxide, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2, 3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether) tetrabromobisphenol A derivative, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2, 3-dibromopropyl ether) tetrabromobisphenol S derivative, tetrabromophthalic anhydride, tetrabromophthalimide, ethylenebistetrabromophthalimide, tetrabromophthalic anhydride derivative, tetrabromophthalic anhydride derivative, tetrabromophthalic acid bis (bis-bromophthalimide), tetrabromophthalic anhydride, tetrabromophthalic acid, Hexabromocyclododecane, decabromodiphenyl ether, decabromodiphenylethane, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylenebistriphenylphenyl ether, ethylenebistentabromophenyl ether, tetradecbromopropanediol, brominated polycarbonate, brominated epoxy resin, polypentabromophenyl methacrylate, brominated polyphenylene oxide, poly-2, 6-dibromophenyl ether, octabromonaphthalene, pentabromocyclohexane, bis (tribromophenyl) fumaramide, or N-methyl hexabromodiphenylamine;
preferably, the brominated flame retardant is selected from at least one of brominated polystyrene or brominated polyphenylene ether; the preferable bromine-based flame retardant has higher CTI.
The flame-retardant synergist is at least one of antimony white and zinc borate.
Wherein, the content range of the brominated flame retardant is 8-35 parts, and the flame retardant synergist is 2-8 parts.
The optional metal salt may be lithium chloride, lithium carbonate, lithium sulfate, lithium acetate, sodium chloride, sodium carbonate, sodium nitrate, sodium sulfate, sodium acetate, potassium chloride, potassium carbonate, potassium sulfate, potassium acetate, calcium chloride, calcium carbonate, calcium sulfate, calcium acetate, zinc chloride, zinc carbonate, zinc sulfate, zinc acetate, copper chloride, copper carbonate, copper sulfate, copper acetate, and the like.
Preferably, the metal ions are selected from at least one of calcium ions, copper ions and zinc ions; more preferably, the metal ion is at least one selected from the group consisting of calcium ion and copper ion. The divalent metal ion is preferable, and the technical effect of inhibiting cyclodextrin or its derivative is better.
The polyamide resin is formed by gradually polycondensing diamine and dibasic acid, or ring-opening polymerization of lactam, or gradual polycondensation of amino acid, or copolymerization of diamine, dibasic acid, lactam and amino acid; the polyamide resin is selected from one or more of PA46, PA66, PA6, PA11, PA12, PA610, PA612, PA1010, PA1012, PA1212, PA4T, PA6T, PA9T, PA10T, PA6I, PAMXD6, PA6I, PA66/6, PA6/66 and PA6T/6I, PA 6T/66.
0-2 parts of additives such as an antioxidant, a lubricant and the like can be added according to the needs to meet the use requirements under certain environments.
The preparation method of the polyamide composition comprises the following steps: weighing the components according to the proportion, premixing the components in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw barrel is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm; carrying out injection molding on the extruded and granulated particles, wherein the injection molding temperature is 270-300 ℃, and the injection molding pressure is 55-100 MPa; and (3) carrying out irradiation crosslinking treatment on the injection molded part, wherein an electron beam is used as a radiation source in the treatment process, and the irradiation dose is 15-25 Mrad, so that the polyamide composition is obtained.
The polyamide composition is applied to preparing light and thin parts such as anti-creeping films, electronic and electric appliance shells and the like.
The invention has the following beneficial effects
The polyamide composition aims to overcome the defects that the fluidity of the polyamide composition is insufficient after irradiation crosslinking and the anti-creeping performance is reduced after multiple processing. According to the invention, a certain amount of cyclodextrin or derivatives thereof are added, and the cyclodextrin or the derivatives thereof are dispersed in the middle of a cross-linking structure to increase the free volume of molecules, so that the chain movement capacity is improved, namely, the melt fluidity is increased, and the defect of poor leak resistance after multiple melting processing is overcome. Furthermore, cyclodextrin or its derivatives, although having a high melting point, are decomposed during high-temperature melt processing to produce small-molecule oxides, which precipitate during long-term use and affect appearance and performance. Therefore, the present invention can inhibit decomposition and precipitation of cyclodextrin by adding a certain amount of metal salt.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw material sources used in the examples and comparative examples are as follows:
PA 66: 85XFS, carnot usa;
PA 10T: vicnyl 700, golden hair science;
PA 1010: g150, wide range of Shandong;
TMAIC: FARIDA H-2, Farlinda Chemicals, Inc.
Beta-cyclodextrin: Sigma-Aldrich;
gamma-cyclodextrin: Sigma-Aldrich.
Lithium acetate: is sold on the market;
sodium chloride: is sold on the market;
potassium carbonate: is sold on the market;
calcium chloride: is sold on the market;
calcium acetate: is sold on the market;
zinc chloride: is sold on the market;
copper chloride: is sold on the market;
copper sulfate: is sold on the market;
iron chloride: it is commercially available.
Brominated polystyrene: PBS-64HW, Kozon;
decabromodiphenylethane: FR-1410, Guangzhou green bird chemical industry;
tetrabromobisphenol S: FR-1524, Guangzhou green bird chemical industry;
antimony white: S-05N, antimony Limited, Chanchen;
zinc borate: HT-207, Fine chemical engineering of Thaixing, Jinan.
Antioxidant: hindered phenolic antioxidant, Irganox 1098.
Examples and comparative examples preparation of polyamide compositions: weighing polyamide resin, an irradiation crosslinking agent, cyclodextrin or a derivative thereof, metal salt and a flame retardant according to a proportion, premixing in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain a finished piece; wherein the length-diameter ratio of a screw of the double-screw extruder is 44:1, the temperature of a screw cylinder is 240-300 ℃, and the rotating speed of the screw is 360 rpm; performing injection molding on the extruded and granulated polyamide composite material (performing injection molding on the extruded and granulated polyamide composite material into a square plate according to the test requirement in the precipitation test of the examples and the comparative examples), wherein the injection molding temperature is 270-300 ℃, and the injection molding pressure is 55-100 MPa; and (3) carrying out irradiation crosslinking treatment on the workpiece, wherein an electron beam is used as a radiation source in the treatment process, and the irradiation dose is 20Mrad, so that the polyamide composition is obtained.
The performance test method comprises the following steps:
(1) CTI test: the polyamide composition surface withstood 50 drops of electrolyte (0.1% aqueous ammonium chloride solution, analytically pure anhydrous ammonium chloride reagent having a mass fraction of about 0.1% purity of not less than 99.8% dissolved in deionized water having a conductivity of not more than 1mS/m and a resistivity of 3.95. omega. m. + -. 0.052. omega. m at 23 ℃. + -. 1 ℃) without the highest voltage value of formation of tracking in V. The CTI performance test was carried out according to the relevant provisions in standard IEC-60112, with a sample thickness of not less than 3 mm.
(2) CTI stability test: the polyamide composition is repeatedly melted and injected at the temperature of 240-320 ℃ (the injection temperature is determined according to the melting point of the polyamide composition), then a sample is crushed, and the CTI value after repeated melting and injection for 3 times is tested, wherein the closer the numerical value is to the CTI of the raw material, the better the stability is.
(3) Melt index: according to the melting point T of the polyamide compositionm+20 ℃ melt flow rate under the action of a 2.16kg weight.
(4) And (3) testing the precipitation property: the composition is injected into a square plate with the thickness of 100 multiplied by 1mm, the square plate is placed in an environment box with the temperature of 85 ℃ and the relative humidity of 85 percent for 100 hours, the square plate is divided into 5 grades according to the degree of precipitates, and the grade 1 represents that no precipitates exist; level 2 represents no visible precipitation, but the surface was found to be marked by wiping; grade 3 indicates that slight precipitation is visible to the naked eye; level 4 indicates significant precipitates; grade 5 indicates severe precipitation.
Table 1: EXAMPLES 1-5 Polyamide compositions in respective component proportions (parts by weight) and test results
Example 1 Example 2 Example 3 Example 4 Example 5
PA66 100 100
PA10T 100 100
PA1010 100
TMAIC 2 2 2 2 2
Beta-cyclodextrin 1 1 1 1
Gamma-cyclodextrin 1
Lithium acetate 0.2 0.2 0.2 0.2 0.2
Antioxidant agent 0.2
CTI，V 575 575 550 575 575
CTI stability test, V 550 550 525 525 550
Melt index, g/10min 15.7 12.1 23.6 12.3 15.6
Precipitation grade 2 1 1 2 2
Examples 1-4 in table 1 also included 15 parts brominated polystyrene, 4 parts antimony white, 7 parts zinc borate; example 5 also included 25 parts of brominated polystyrene, 4 parts of antimony white, and 3 parts of zinc borate.
As shown in example 1/4, gamma-cyclodextrin was more easily eluted, resulting in slightly inferior CTI stability and elution level.
Table 2: EXAMPLES 6-12 Polyamide compositions in respective component proportions (parts by weight) and test results
Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12
PA66 100 100 100 100 100 100 100
TMAIC 2 2 2 2 2 2 2
Beta-cyclodextrin 0.1 0.2 0.3 0.5 0.6 0.9 2
Lithium acetate 0.05 0.1 0.15 0.3 0.4 0.6 1
CTI，V 575 575 575 575 575 575 550
CTI stability test, V 525 550 575 575 575 550 525
Melt index, g/10min 7.5 10.4 11.7 12.5 14.0 18.6 25
Precipitation grade 2 1 1 1 1 1 2
Each of the examples in table 2 also included 15 parts of brominated polystyrene, 4 parts of antimony white, and 7 parts of zinc borate.
From examples 1/6-12, it is clear that the addition amount of cyclodextrin and metal salt increases the fluidity of the composition, and that the CTI stability is better and the precipitation is less in the preferable addition amount.
Table 3: EXAMPLES 13 to 19 Polyamide compositions in respective component proportions (parts by weight) and test results
Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19
PA66 100 100 100 100 100 100 100
TMAIC 2 2 2 2 2 2 2
Beta-cyclodextrin 1 1 1 1 1 1 1
Sodium chloride 0.2
Potassium carbonate 0.2
Calcium chloride 0.2
Calcium acetate 0.2
Zinc chloride 0.2
Copper chloride 0.2
Copper sulfate 0.2
CTI，V 575 575 575 575 575 575 575
CTI stability test, V 550 550 575 575 550 575 575
Melt index, g/10min 11 10.8 15.2 12.9 14.1 16.5 11.4
Precipitation grade 2 2 1 1 1 1 1
Each of the examples in table 3 also included 15 parts of brominated polystyrene, 4 parts of antimony white, and 7 parts of zinc borate.
As is clear from comparison of examples 1 and 13 to 19, the metal ions are preferably calcium ions, copper ions and zinc ions, more preferably calcium ions and copper ions, and have better CTI stability and precipitation resistance.
Table 4: EXAMPLES 20 to 21 Polyamide compositions in respective component proportions (parts by weight) and test results
Example 20 Example 21
PA66 100 100
Brominated polystyrene
Decabromodiphenylethane 15
Tetrabromobisphenol S 15
Antimony white 4 4
Zinc borate 7 7
TMAIC 2 2
Beta-cyclodextrin 0.5 0.5
Lithium acetate 0.3 0.3
CTI，V 550 550
CTI stability test, V 550 550
Melt index, g/10min 20.5 23.7
Precipitation grade 1 1
From examples 9/20-21, it is clear that the preferred brominated flame retardant has a higher CTI.
Table 5: comparative example Polyamide composition the proportions (parts by weight) of the components and the results
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
PA66 100 100 100 100 100 100
TMAIC 2 2 2 2 2 2
Beta-cyclodextrin 0.5 1 3 1
Lithium acetate 1 1
Ferric chloride 0.2
CTI，V 600 575 550 475 550 550
CTI stability test, V 475 475 425 400 425 425
Melt index, g/10min 2.8 9 12 28 3.5 10.4
Precipitation grade 1 3 3 4 1 3
Each of the comparative examples in table 5 also included 15 parts of brominated polystyrene, 4 parts of antimony white, and 7 parts of zinc borate.
From the examples and comparative example 1, it is known that the addition of cyclodextrin and metal salt can significantly improve the CTI stability and have higher practicability although the addition of cyclodextrin and metal salt can reduce the CTI to a certain extent.
As shown in the comparative example 2/3, cyclodextrin needs to be added together with metal salt in a compounding manner, so that the decomposition and precipitation of cyclodextrin are avoided, and the CTI stability is further ensured.
As can be seen from comparative example 4, the amount of cyclodextrin added should not be outside the scope of the present invention.

Claims (10)

1. The polyamide composition is characterized by comprising the following components in parts by weight:
100 parts of polyamide resin;
10-40 parts of a flame retardant;
0.01-10 parts of irradiation crosslinking agent;
0.1-2 parts of cyclodextrin or cyclodextrin derivative;
0.05-1.5 parts of metal salt;
the polyamide composition has a cross-linking structure among polyamide molecules;
the flame retardant is a brominated flame retardant/flame retardant synergist compound system;
the metal ion of the metal salt is selected from at least one of lithium ion, sodium ion, potassium ion, calcium ion, zinc ion or copper ion, and the anion paired with the metal ion is selected from at least one of halogen ion, carbonate ion, nitrate ion, sulfate ion or acetate ion.
2. The polyamide composition of claim 1, wherein the cyclodextrin or the derivative thereof is present in an amount of 0.2 to 0.9 parts, and the metal salt is present in an amount of 0.1 to 0.6 parts; more preferably, the content of the cyclodextrin or the derivative thereof is 0.3 to 0.6 part, and the content of the metal salt is 0.15 to 0.4 part.
3. The polyamide composition of claim 1, wherein the radiation crosslinking agent is at least one member selected from the group consisting of triallyl cyanurate, triallylisocyanurate, methyl triallylisocyanurate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, and dipropylene glycol diacrylate.
4. The polyamide composition of claim 1, wherein the cyclodextrin or derivative thereof is selected from at least one of β -cyclodextrin, γ -cyclodextrin, hydroxypropyl- β -cyclodextrin, sulfobutyl ether- β -cyclodextrin, disaccharide- β -cyclodextrin, methyl- β -cyclodextrin, or hydroxyethyl- β -cyclodextrin; preferably, the cyclodextrin or its derivative is selected from beta-cyclodextrin.
5. The polyamide composition of claim 4, wherein the brominated flame retardant is selected from the group consisting of brominated polystyrene, polybrominated styrene, brominated polyphenylene ether, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromobiphenyl, hexabromobiphenyl oxide, octabromobiphenyl oxide, decabromobiphenyl oxide, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2, 3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether) tetrabromobisphenol A derivative, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2, 3-dibromopropyl ether) tetrabromobisphenol S derivative, tetrabromophthalic anhydride, tetrabromophthalimide, tetrabromobisphenol S, tetrabromophthalimide, and mixtures thereof, At least one of ethylenebistetrabromophthalimide, tetrabromophthalic anhydride derivative, hexabromocyclododecane, decabromodiphenyl ether, decabromodiphenylethane, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylenebistriphenylphenyl ether, ethylenebistentabromophenyl ether, tetradecbromopropanediol, brominated polycarbonate, brominated epoxy resin, polypentabromophenyl methacrylate, brominated polyphenylene oxide, poly-2, 6-dibromophenyl ether, octabromonaphthalene, pentabromocyclohexane, bis (tribromophenyl) fumaramide, or N-methyl hexabromodiphenylamine; preferably, the brominated flame retardant is selected from at least one of brominated polystyrene or brominated polyphenylene ether; the flame-retardant synergist is at least one of antimony white and zinc borate; the content range of the brominated flame retardant is 8-35 parts, and the flame retardant synergist is 2-8 parts.
6. Polyamide composition according to claim 1, characterized in that the metal ions are selected from at least one of calcium, copper or zinc ions; more preferably, the metal ion is at least one selected from the group consisting of calcium ion and copper ion.
7. The polyamide composition as claimed in claim 1, wherein the polyamide resin is obtained by stepwise polycondensation of diamine and dibasic acid, or ring-opening polymerization of lactam, or stepwise polycondensation of amino acid, or copolymerization of diamine, dibasic acid, lactam and amino acid; the polyamide resin is selected from one or more of PA46, PA66, PA6, PA11, PA12, PA610, PA612, PA1010, PA1012, PA1212, PA4T, PA6T, PA9T, PA10T, PA6I, PAMXD6, PA6I, PA66/6, PA6/66, PA6T/6I or PA 6T/66.
8. The polyamide composition of claim 1, further comprising 0-2 parts of one or more of an antioxidant and a lubricant.
9. Process for the preparation of a polyamide composition according to any one of claims 1 to 8, characterized in that it comprises the following steps: weighing the components according to the proportion, premixing the components in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw barrel is 240-300 ℃, and the rotating speed of the screw is 200-550 rpm; carrying out injection molding on the extruded and granulated particles, wherein the injection molding temperature is 270-300 ℃, and the injection molding pressure is 55-100 MPa; and (3) carrying out irradiation crosslinking treatment on the injection molded part, wherein an electron beam is used as a radiation source in the treatment process, and the irradiation dose is 15-25 Mrad, so that the polyamide composition is obtained.
10. Use of a polyamide composition according to any one of claims 1 to 8 for the production of light and thin parts.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015113740A1 (en) * 2014-01-29 2015-08-06 Clariant International Ltd Halogen-free solid flame retardant mixture and use thereof
WO2017131008A1 (en) * 2016-01-29 2017-08-03 東洋紡株式会社 Heat-resistant polyamide resin composition
CN108329678A (en) * 2018-01-12 2018-07-27 金发科技股份有限公司 A kind of Amilan polyamide resin composition and preparation method thereof
CN108727810A (en) * 2018-05-23 2018-11-02 江苏金发科技新材料有限公司 Long glass fiber reinforced daiamid composition and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015113740A1 (en) * 2014-01-29 2015-08-06 Clariant International Ltd Halogen-free solid flame retardant mixture and use thereof
WO2017131008A1 (en) * 2016-01-29 2017-08-03 東洋紡株式会社 Heat-resistant polyamide resin composition
CN108329678A (en) * 2018-01-12 2018-07-27 金发科技股份有限公司 A kind of Amilan polyamide resin composition and preparation method thereof
CN108727810A (en) * 2018-05-23 2018-11-02 江苏金发科技新材料有限公司 Long glass fiber reinforced daiamid composition and preparation method thereof

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