CN106916441A - A kind of carbon fiber reinforcement non-bittern system flame-retardant PA 66 composite and preparation method - Google Patents

A kind of carbon fiber reinforcement non-bittern system flame-retardant PA 66 composite and preparation method Download PDF

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Publication number
CN106916441A
CN106916441A CN201510995630.1A CN201510995630A CN106916441A CN 106916441 A CN106916441 A CN 106916441A CN 201510995630 A CN201510995630 A CN 201510995630A CN 106916441 A CN106916441 A CN 106916441A
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retardant
flame
carbon fiber
phosphorus
fibre reinforced
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Inventor
马海清
刘刚
林航
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Heilongjiang Xinda Enterprise Group Co Ltd
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Heilongjiang Xinda Enterprise Group Co Ltd
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Priority to CN201510995630.1A priority Critical patent/CN106916441A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of carbon fiber reinforcement non-bittern flame-proof PA66 composites and preparation method thereof, the composite is grouped into by each group of following weight percentage：PA6652.1 ~ 68.1%, halogen-free flame retardants 15 ~ 20%, carbon fiber 10 ~ 30%, graft type plasticized modifier 2 ~ 4%, antioxidant 0.4%, lubrication dispersing agent 0.5%.The invention further relates to foregoing carbon fiber reinforcement non-bittern flame-proof PA66 composites and preparation method thereof, there is particular/special requirement to develop the antistatic and flame-retardant performance of the anti-electromagnetic shielding requirements of material the present invention be directed to electric type product, compared with prior art, product high mechanical strength of the invention, sheet resistance reaches 10-2-106Ω, anti-electromagnetic shielding, halogen-free environmental reaches UL-94V0, and apparent excellent comprehensive performance is excellent, is particularly well-suited to rigorous thin wall parts high.

Description

A kind of carbon fiber reinforcement non-bittern system flame-retardant PA 66 composite and preparation method
Technical field
The present invention relates to a kind of nylon composite materials, more particularly, to the present invention relates to a kind of fibre reinforced phosphorous flame-retardant PA66 composites and preparation method thereof.
Background technology
PA66 has good mechanical strength, good fluidity, is particularly well-suited to the application on thin wall parts.Increase for fiber Strong PA66 is flame-retardant modified, and traditional bromine sb system flame retarding efficiency is high, and property retention rate is good, but easily form secondary pollution and gradually by Eliminate.Modern humans' environmental protection concept is more and more stronger, and phosphorus flame retardant is trend of the times.Although red phosphorus combustion inhibitor excellent in efficiency but possibility The risk of product corrosion failure, external phosphorus flame retardant good combination property but selling at exorbitant prices, limitation caused by fire retardant is separated out It is used.The present invention determines phosphorus content ＞ 30%, nitrogen content ＞ 5%, phosphorus-nitrogen ratio 4 using the phosphorus-nitrogen containing flame retardant of compounding:1 Flame retardant formulations, the flame retardant effect being optimal.
Antistatic modified aspect, addition low-molecular-weight antistatic additive is most common antistatic measure, this material modified The moisture reduction surface resistivity for mainly using antistatic additive to be adsorbed in material surface, therefore poor durability, it is not washable, to ring The dependence of border humidity is big, and foreign countries have scholar that the metal salt sol of certain component, metal are combined in the polymer containing ehter bond The ehter bond of ion and polyether block thing coordinates, and ionic conduction network is internally formed at it, improves conductance, strengthens leading for polymer Electric energy power, both approaches have decline in various degree to the heat resisting temperature and surface characteristic of material, and do not apply to strengthens with enhancing Material.And through carbon black, the modified polymer of metal packing, though relatively good permanence antistatic performance can be obtained, often adds Dosage is big, and performance destroys big and processing difficulties.
The content of the invention
The purpose of the present invention is exactly to provide a kind of fibre reinforced phosphorus for the defect for overcoming above-mentioned prior art to exist It is the preparation method of flame-retardant PA 66 composite.
The purpose of the present invention can be achieved through the following technical solutions：
In a first aspect, the present invention relates to a kind of fibre reinforced phosphorous flame-retardant PA66 composites, the composite is by following The each group of weight percentage is grouped into：
PA66 52.1 ~ 68.1%,
Phosphorus flame retardant 15 ~ 20%,
Carbon fiber 10 ~ 30%,
Graft type plasticized modifier 2 ~ 4%,
Antioxidant 0.4%,
Lubrication dispersing agent 0.5%.
Preferably, the PA66 is common injection grade resins, and the viscosity of PA66 resins is 0.7 ~ 1.5Pa.s.
Preferably, the phosphorus flame retardant is nitrogen phosphorus system compound flame redundant, wherein：With nitrogen phosphorus system compound flame redundant matter Amount content is counted for 100%, phosphorus >=30%, nitrogen >=5%, and phosphorus is 4 with the mass content ratio of nitrogen:1.
Preferably, the nitrogen phosphorus system compound flame redundant is that hypophosphites is compounded with expansion type phosphor nitrogenated flame retardant.
Preferably, the hypophosphites is in diethyl hypophosphites, ethyl hypophosphites, ethyl-butyl hypophosphites One or several mixture.
Preferably, the expansion type phosphor nitrogenated flame retardant is melamine cyanurate, melamine pyrophosphate, phosphoric acid The mixing of one or more of ammonium, phosphonitrile, pyrrolotriazine derivatives.
Preferably, the carbon fiber is modified chopped carbon fiber, and its length is 4 ~ 7mm.
Preferably, the carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/mm3, stretch modulus ＞ 250G.Pa。
Preferably, the antioxidant is antioxidant 245.
Preferably, the graft type plasticized modifier is ethene and octene graft copolymer.
Preferably, the lubrication dispersing agent is silicone.
Second aspect, the invention further relates to the preparation method of foregoing fibre reinforced phosphorous flame-retardant PA66 composites, Methods described comprises the following steps：
1) got the raw materials ready according to following rent=component and weight percent content：
PA66 52.1 ~ 68.1%,
Phosphorus flame retardant 15 ~ 20%,
Carbon fiber 10 ~ 30%,
Graft type plasticized modifier 2 ~ 4%,
Antioxidant 0.4%,
Lubrication dispersing agent 0.5%；
2) discharged after above-mentioned raw materials being put into 3 ~ 5min of high-speed mixer and mixing, obtain mixture, carbon fiber is added from side spout, Then 210 ~ 240 DEG C of the processing temperature of double screw extruder is controlled, mixture is placed in double spiral shells by 180 ~ 600 revs/min of screw rod revolution Bar extruder extruding pelletization, you can.
Compared with prior art, the present invention has following excellent effect：
1) present invention is using the phosphorus system phosphorus-nitrogen containing flame retardant for compounding, and hypophosphites is multiple in proportion with expansion type phosphor nitrogenated flame retardant Match somebody with somebody, final phosphorus >=30%, nitrogen >=5%, phosphorus nitrogen mass ratio 4:1, the flame retardant effect being optimal, compounding overcomes domestic single phosphorus system Fire retardant efficiency is low, resistance to temperature difference inferior position, compared with phosphorus flame retardant known to foreign countries, reaches equal flame retardant effect, into This is lower.
2) the specially treated carbon fiber that the present invention is used has good as conductive reinforced modifier with thermoplastic resin Good associativity, carbon fiber has the features such as light weight, tensile strength high, wear-resistant, corrosion-resistant, creep resistant, conduction, heat transfer sheet, Compared with glass fibre, modulus is high 3 ~ 5 times, is a kind of excellent reinforcing material for obtaining high rigidity and high-strength nylon material.Profit Its electric conductivity is used, conductive material electrical efficiency high-mechanical property conductive carbon black filler high, traditional, carbon black and resin knot is prepared Close poor dispersion, bad mechanical property, the infringement part that comes off easy to wear.
3) have special to the antistatic and flame-retardant performance of the anti-electromagnetic shielding requirements of material the present invention be directed to electric type product It is required that developing, product surface resistance of the invention reaches 10-2-106Ω, anti-electromagnetic shielding, phosphorus system environmental protection reaches UL-94V0, machine Tool intensity is high, and apparent excellent comprehensive performance is excellent, with reference to the good mobile performances of PA66, is particularly well-suited to high thin of rigorous Wall product.
Specific embodiment
With reference to specific embodiment to the detailed description of the invention.Following examples will be helpful to those skilled in the art The present invention is further understood, but the invention is not limited in any way.It should be pointed out that to this area Dare ordinary skill people For member, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to of the invention Protection domain.
Embodiment 1
The present embodiment is related to a kind of preparation method of fibre reinforced phosphorous flame-retardant PA66 composites, comprises the following steps：
Step 1, is got the raw materials ready according to the component and content in table 1：
Wherein：
PA66 is the refreshing horse EPR2700 in Jiangsu；
Phosphorus flame retardant is that diethyl hypophosphites presses 5 with melamine cyanurate:The compound resistance of nitrogen phosphorus system of 1 compounding Combustion agent, wherein phosphorus content >=30%, nitrogen content >=5%, phosphorus nitrogen content ratio is 4:1；
Carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/mm3, stretch modulus ＞ 250G.Pa；
Graft type plasticized modifier is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, preferably It is Arkema AX8900；
Antioxidant is antioxidant 245；
Lubrication dispersing agent is silicone；
Step 2, above-mentioned raw materials is put into after 3 ~ 5min of high-speed mixer and mixing and is discharged, and obtains mixture, and carbon fiber is from side spout Add, then control 210 ~ 240 DEG C of the processing temperature of double screw extruder, 180 ~ 600 revs/min of screw rod revolution puts mixture In double screw extruder extruding pelletization, product is obtained final product.
Embodiment 2
PA66 is the refreshing horse EPR2700 in Jiangsu；
The present embodiment is related to a kind of preparation method of fibre reinforced phosphorous flame-retardant PA66 composites, comprises the following steps：
Step 1, is got the raw materials ready according to the component and content in table 1：
Wherein：
Phosphorus flame retardant is that ethyl hypophosphites presses 6 with melamine pyrophosphate:The nitrogen phosphorus system of 1 compounding is compound fire-retardant Agent, wherein phosphorus content >=30%, nitrogen content >=5%, phosphorus nitrogen content ratio is 4:1；
Carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/mm3, stretch modulus ＞ 250G.Pa；
Graft type plasticized modifier is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, preferably It is Arkema AX8900；
Antioxidant is antioxidant 245；
Lubrication dispersing agent is silicone；
Step 2, above-mentioned raw materials is put into after 3 ~ 5min of high-speed mixer and mixing and is discharged, and obtains mixture, and carbon fiber is from side spout Add, then control 210 ~ 240 DEG C of the processing temperature of double screw extruder, 180 ~ 600 revs/min of screw rod revolution puts mixture In double screw extruder extruding pelletization, product is obtained final product.
Embodiment 3
PA66 is the refreshing horse EPR2700 in Jiangsu；
The present embodiment is related to a kind of preparation method of fibre reinforced phosphorous flame-retardant PA66 composites, comprises the following steps：
Step 1, is got the raw materials ready according to the component and content in table 1：
Wherein：
Phosphorus flame retardant is that ethyl-butyl hypophosphites presses 6 with ammonium phosphate:The nitrogen phosphorus system composite fire retardant of 1 compounding, its Middle phosphorus content >=30%, nitrogen content >=5%, phosphorus nitrogen content ratio is 4:1；
Carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/mm3, stretch modulus ＞ 250G.Pa；
Graft type plasticized modifier is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, preferably It is Arkema AX8900；
Antioxidant is antioxidant 245；
Lubrication dispersing agent is silicone；
Step 2, above-mentioned raw materials is put into after 3 ~ 5min of high-speed mixer and mixing and is discharged, and obtains mixture, and carbon fiber is from side spout Add, then control 210 ~ 240 DEG C of the processing temperature of double screw extruder, 180 ~ 600 revs/min of screw rod revolution puts mixture In double screw extruder extruding pelletization, product is obtained final product.
Embodiment 4
The present embodiment is related to a kind of preparation method of fibre reinforced phosphorous flame-retardant PA66 composites, comprises the following steps：
Step 1, is got the raw materials ready according to the component and content in table 1：
Wherein：
PA66 is the refreshing horse EPR2700 in Jiangsu；
Phosphorus flame retardant is that diethyl hypophosphites presses 6 with the mixture of ethyl hypophosphites with melamine cyanurate:1 answers With nitrogen phosphorus system composite fire retardant, wherein phosphorus content >=30%, nitrogen content >=5%, phosphorus nitrogen content ratio is 4:1；
Carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/mm3, stretch modulus ＞ 250G.Pa；
Graft type plasticized modifier is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, preferably It is Arkema AX8900；
Antioxidant is antioxidant 245；
Lubrication dispersing agent is silicone；
Step 2, above-mentioned raw materials is put into after 3 ~ 5min of high-speed mixer and mixing and is discharged, and obtains mixture, and carbon fiber is from side spout Add, then control 210 ~ 240 DEG C of the processing temperature of double screw extruder, 180 ~ 600 revs/min of screw rod revolution puts mixture In double screw extruder extruding pelletization, product is obtained final product.
Comparative example 1 ~ 4
Following comparative example all refers to the preparation method of PA66 composites, comprises the following steps：
Step 1, is got the raw materials ready according to the component and content in table 2；
Wherein：
PA66 is the refreshing horse EPR2700 in Jiangsu；
Phosphorus flame retardant is Clariant OP1312；
Antioxidant is antioxidant 245；
Lubrication dispersing agent is silicone；
Glass fibre is megalith group GF988A；
Carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/mm3, stretch modulus ＞ 250G.Pa；
Graft type plasticized modifier is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, preferably It is Arkema AX8900；
Step 2, above-mentioned raw materials is put into after 3 ~ 5min of high-speed mixer and mixing and is discharged, and obtains mixture, and carbon fiber is from side spout Add, then control 210 ~ 240 DEG C of the processing temperature of double screw extruder, 180 ~ 600 revs/min of screw rod revolution puts mixture In double screw extruder extruding pelletization, product is obtained final product.
Table 1
Raw material/wt% Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
PA66 67.1 55.1 52.1 68.1
Phosphorus flame retardant 20 17 15 17
Carbon fiber 10 25 30 10
Graft type plasticized modifier 2 2 2 4
Antioxidant 0.4 0.4 0.4 0.4
Lubrication dispersing agent 0.5 0.5 0.5 0.5
Table 2
Raw material/wt% Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
PA66 52.8 45.8 42.8 59.8
Glass fibre 40.3 30.3 33.3
Carbon fiber 16.3
Phosphorus flame retardant 17
External phosphorus flame retardant 17
Plasticized modifier 2 2 2 2
Conductive black 4 4 4 4
Antioxidant 0.4 0.4 0.4 0.4
Lubrication dispersing agent 0.5 0.5 0.5 0.5
The sample 1 ~ 8 according to obtained in embodiment 1 ~ 4 and comparative example 1 ~ 4, carries out performance test comparison, using iso standard, testability Can contrast as shown in table 3.
Table 3
Test event Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Sample 8
Tensile strength/MPa 95 125 155 120 95 80 85 130
Bending strength/MPa 180 220 245 210 160 170 170 225
Bending modulus/MPa 6000 900 12000 8800 7500 6500 6300 9100
6.5 8.0 8.5 9.2 6.5 5.5 6.0 8.5
Anti-flammability（UL94）/1.6mm V0 V0 V0 V0 HB V0 V0 V0
Product phosphorus system environmental protection obtained in embodiment 1 ~ 4 reaches UL-94V0, and high mechanical strength, apparent excellent comprehensive performance is excellent, with Comparative example 1 ~ 4 is compared, and the addition mechanical performance destruction of conductive black is big, continues to increase carbon black conductive carbon black addition, and processing is tired Difficulty, prepared sample apparent mass is poor, not practical.Compared with external fire retardant, mechanical performance is substantially suitable, and cost is more It is low.Specific embodiment of the invention is described above.It is to be appreciated that the invention is not limited in above-mentioned specific reality Mode is applied, those skilled in the art can within the scope of the claims make various deformations or amendments, and this has no effect on this hair Bright substance.

Claims (10)

1. a kind of fibre reinforced phosphorous flame-retardant PA66 composites, it is characterised in that the composite is by following weight hundred The each group of point content is grouped into：
PA66 52.1 ~ 68.1%,
Phosphorus flame retardant 15 ~ 20%,
Carbon fiber 10 ~ 30%,
Graft type plasticized modifier 2 ~ 4%,
Antioxidant 0.4%,
Lubrication dispersing agent 0.5%.
2. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 1, it is characterised in that the PA66 is Common injection grade resins, the viscosity of PA66 resins is 0.7 ~ 1.5Pa.s.
3. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 1, it is characterised in that the phosphorus system resistance Combustion agent is nitrogen phosphorus system compound flame redundant, wherein：Counted as 100% with nitrogen phosphorus system compound flame redundant mass content, phosphorus >=30%, nitrogen >=5%, phosphorus is 4 with the mass content ratio of nitrogen:1.
4. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 3, it is characterised in that the nitrogen phosphorus system Compound flame redundant is that hypophosphites is compounded with expansion type phosphor nitrogenated flame retardant.
5. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 4, it is characterised in that the hypophosphorous acid Salt is one or several the mixture in diethyl hypophosphites, ethyl hypophosphites, ethyl-butyl hypophosphites.
6. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 4, it is characterised in that the intumescent Phosphorus-nitrogen containing flame retardant is melamine cyanurate, melamine pyrophosphate, ammonium phosphate, phosphonitrile, one kind of pyrrolotriazine derivatives Or several mixing.
7. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 1, it is characterised in that the carbon fiber It is the chopped carbon fiber that is modified, its length is 4 ~ 7mm, and carbon fiber is polyacrylonitrile-based carbon fibre, its tensile strength ＞ 500kg/ mm3, stretch modulus ＞ 250G.Pa.
8. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 1, it is characterised in that the antioxidant It is antioxidant 245, lubrication dispersing agent is silicone.
9. fibre reinforced phosphorous flame-retardant PA66 composites according to claim 1, it is characterised in that the graft type Plasticized modifier is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
10. a kind of preparation method of fibre reinforced phosphorous flame-retardant PA66 composites as claimed in claim 1, its feature exists In methods described comprises the following steps：
Got the raw materials ready according to following components and weight percent content：
PA66 52.1 ~ 68.1%,
Phosphorus flame retardant 15 ~ 20%,
Carbon fiber 10 ~ 30%,
Graft type plasticized modifier 2 ~ 4%,
Antioxidant 0.4%,
Lubrication dispersing agent 0.5%；
Discharged after above-mentioned raw materials are put into 3 ~ 5min of high-speed mixer and mixing, obtain mixture, carbon fiber is added from side spout, so Double screw extruder extruding pelletization is controlled afterwards, you can.
CN201510995630.1A 2015-12-28 2015-12-28 A kind of carbon fiber reinforcement non-bittern system flame-retardant PA 66 composite and preparation method Pending CN106916441A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110183846A (en) * 2019-05-10 2019-08-30 南通开普乐工程塑料有限公司 A kind of high wear-resistant carbon fiber reinforcement PA66 and preparation method thereof
CN111100446A (en) * 2018-10-26 2020-05-05 汉达精密电子(昆山)有限公司 High-performance PA66 composite material and product thereof
CN112409786A (en) * 2020-10-12 2021-02-26 金发科技股份有限公司 Low-mold-fouling halogen-free flame-retardant thermoplastic polyamide composition and preparation method and application thereof
CN113882143A (en) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 Flame-retardant polyacrylonitrile fiber and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100446A (en) * 2018-10-26 2020-05-05 汉达精密电子(昆山)有限公司 High-performance PA66 composite material and product thereof
CN110183846A (en) * 2019-05-10 2019-08-30 南通开普乐工程塑料有限公司 A kind of high wear-resistant carbon fiber reinforcement PA66 and preparation method thereof
CN113882143A (en) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 Flame-retardant polyacrylonitrile fiber and preparation method thereof
CN112409786A (en) * 2020-10-12 2021-02-26 金发科技股份有限公司 Low-mold-fouling halogen-free flame-retardant thermoplastic polyamide composition and preparation method and application thereof
WO2022077865A1 (en) * 2020-10-12 2022-04-21 金发科技股份有限公司 Low-mold deposit halogen-free flame-retardant thermoplastic polyamide composition, and preparation method therefor and application thereof
CN112409786B (en) * 2020-10-12 2022-05-20 金发科技股份有限公司 Low-mold-scale halogen-free flame-retardant thermoplastic polyamide composition and preparation method and application thereof

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