CN107698798A - Glass fiber enhanced nylon not nitrogenous halogen-free flameproof compound system and its application - Google Patents
Glass fiber enhanced nylon not nitrogenous halogen-free flameproof compound system and its application Download PDFInfo
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- CN107698798A CN107698798A CN201711173632.8A CN201711173632A CN107698798A CN 107698798 A CN107698798 A CN 107698798A CN 201711173632 A CN201711173632 A CN 201711173632A CN 107698798 A CN107698798 A CN 107698798A
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses a kind of not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon, and by weight percentage, raw material composition includes：Diethyl hypo-aluminum orthophosphate 60~90%, aluminium phosphite 9~30% and zinc stannate 1~10%.The invention discloses a kind of not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon, the not nitrogenous halogen-free flameproof compound system has the characteristics that high fire-retardance, non-migratory, not etching apparatus, the defects of overcoming the existing phosphorus nitrogen compounding flame retardant based on diethyl hypo-aluminum orthophosphate applied to glass fiber reinforced nylon material；And glass fiber reinforced nylon material system can be well adapted for, obtain the halogen-free flame-retardant glass fiber enhancing nylon material of excellent combination property.
Description
Technical field
The present invention relates to the technical field of fire retardant, and in particular to a kind of glass fiber enhanced nylon is answered with not nitrogenous halogen-free flameproof
Application with system and its in halogen-free flame-retardant glass fiber strengthens nylon material.
Background technology
Glass fiber enhanced nylon is because with good rigidity and impact resistance, low warpage properties, high dimensional stability, good
The performance characteristics such as appearance and be widely used in field of electronics.Application in these fields, resistance is proposed to material
The requirement of combustion, and nylon is combustible material, with glass it is compound after, due to the wick effect of glass so that glass fiber enhanced nylon
Easily burn.Therefore glass fiber enhanced nylon when these fields are applied, it is necessary to solve the problems, such as fire-retardant, and wick effect
In the presence of make it that its fire-retardant difficulty is bigger.
At present, for the fire-retardant of glass fiber enhanced nylon, including the flame-retardant system that two classes are basic：Halogen system flame-retardant system and non-halogen
Flame-retardant system.Halogen system flame-retardant system is typically brominated flame-retardant collaboration antimony oxide, and numerous studies show, are hindered added with bromine system
Firing the glass fiber reinforced nylon material of agent can produce thick smoke and the harmful substance such as hydrogen bromide in burning, human body can be caused to suffocate.Cause
This, developing safe and environment-friendly, halogen-free flame-retardant system for glass fiber enhanced nylon turns into the focus of research, occurs in recent years new
Halogen-free flame retardants or flame-retardant system applied to glass fiber enhanced nylon.
According to the literature, the halogen-free flame retardants applied to fiberglass reinforced mainly includes two major class primary structures：One kind is red
Phosphorus；Another kind of is phosphorus nitrogen system flame-retardant system.For red phosphorus, although its good flame retardation effect, it faces two problems：First, red phosphorus
Color, limit its application, be generally only to apply in black products；Second, phosphatization is easily produced in process
The violents in toxicity such as hydrogen, environmental protection and safety problem are brought, therefore red phosphorus is not the optimal selection of glass fiber enhanced nylon.For phosphorus nitrogen system
Flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency, it also avoid some defects of red phosphorus, be mesh
The focus of preceding research.
With the most use, the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate, for example, diethyl hypophosphorous acid is answered at present
Aluminium compounds melamine Quadrafos (MPP) system, can be with due to higher phosphorus content, and the synergy of phosphorus nitrogen
The highly effective flame-retardant to glass fiber enhanced nylon is realized, also in the absence of product color problem, while there is very high decomposition temperature, in glass
In the high temperature working processes for strengthening nylon, the hypertoxic gas such as hydrogen phosphide will not be produced.But for based on diethyl hypo-aluminum orthophosphate
Phosphorus nitrogen compound system, however it remains some shortcomings, be mainly manifested in：First, two kinds of components have certain reaction point in high temperature
Solution, produces a small amount of sour gas, and these sour gas can produce corrosion to the metal parts of process equipment, after a certain time
Need to change part, the problem of bringing the increase of cost and reduce production efficiency；Second, there is certain analysis in nitrogen-containing compound MPP
Go out, material is in injection molding process, after being molded the product of certain modulus, there can be deposit on mould, these deposits
Presence can influence the outward appearance of product, at this moment need cleaning mould of stopping work, can also reduce production efficiency, while this precipitation can also
Cause fire retardant to be migrated to product surface, cause fire retardant skewness and loss, the final fire-retardant failure for causing material, exist
Potential safety hazard.
As a whole, it is applied to the flame-retardant system of glass fiber enhanced nylon at present, there are color, produce toxic gas, be easy
Separate out and have the problems such as corrosion, some are that fatal problem causes to use, and some are then to cause cost increase, efficiency to reduce
Deng.Therefore, it is necessary to develop new halogen-free flame-retardant system.
The content of the invention
The present invention is for the existing compounding of the phosphorus nitrogen based on diethyl hypo-aluminum orthophosphate applied to glass fiber reinforced nylon material
The defects of flame-retardant system, a kind of not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon is disclosed, the not nitrogenous Halogen resistance
Combustion compound system has the characteristics that high fire-retardance, non-migratory, not etching apparatus, can be well adapted for glass fiber reinforced nylon material body
System, obtain the halogen-free flame-retardant glass fiber enhancing nylon material of excellent combination property.
Specific technical scheme is as follows：
A kind of not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon, by weight percentage, raw material composition include：
Diethyl hypo-aluminum orthophosphate 60~90%；
Aluminium phosphite 9~30%；
Zinc stannate 1~10%.
The present invention uses diethyl hypo-aluminum orthophosphate, then is assisted by the aluminium phosphite non-migratory with special high temperature resistant and zinc stannate
Together, the compounding flame retardant based on phosphorus constructed of aluminium of non-nitrogen containing is formed, solves perishable, precipitation easy to migrate of existing flame-retardant system etc.
Defect.
The present invention will be elaborated below：
The patent inventor of the present invention is to solve the existing halogen-free flame-retardant system being applied in glass fiber reinforced nylon material
For the purpose of existing various defects, have made extensive and intensive studies.For the existing compounding based on diethyl hypo-aluminum orthophosphate
Flame-retardant system has investigated new flame-retardant system Flame-retardant Glass Fiber Reinforced Pa is present the problem of, as a result finds diethyl hypophosphorous acid
Aluminium cooperates with aluminium phosphite and a small amount of zinc stannate to solve this problem well.
Shown in the chemical constitution of diethyl hypo-aluminum orthophosphate such as following formula (I)：
The characteristics of diethyl hypo-aluminum orthophosphate is phosphorus content height, good flame resistance, has higher temperature of initial decomposition, water-soluble
Low, resistance to migration is nonhygroscopic, and more application is in the engineering plastics such as nylon, PBT at present, particularly engineering plastics of fiberglass reinforced
In.Be used alone diethyl hypo-aluminum orthophosphate, in the absence of separate out the problem of, but its fire resistance deficiency, therefore also need to it is nitrogenous
MPP compounding, can be only achieved fire-retardant ask.The flame-retardant system in glass fiber enhanced nylon is applied substantially with diethyl hypophosphorous acid at present
Aluminium cooperates with MPP systems.
But when with MPP compounding uses, its decomposition temperature can be reduced diethyl hypophosphorous acid, and acid can be discharged in process
Property gas and ammonia, corrosion can be produced to process equipment metal parts, and MPP migration characteristic so that die surface exists heavy
Product thing, outward appearance is influenceed, it is necessary to which periodic cleaning mould, reduces production efficiency.It will be apparent that MPP there are problems that cause these
Key, MPP use is reduced as far as possible or without using MPP.
Inventor herein is had found by studying, and in the presence of diethyl hypo-aluminum orthophosphate, adds suitable amounts
Aluminium phosphite, the flame-retardant system based on phosphorus constructed of aluminium is formed, the system has preferable flame-retarding characteristic.The molecule knot of phosphorous acid
Shown in structure such as following formula (II)：
Aluminium phosphite has very high heat decomposition temperature, while water-soluble low, resistance to migration；It can be assisted with diethyl hypo-aluminum orthophosphate
Same-action solves the problems, such as to separate out and in mold deposits, but improves unobvious, while fire resistance phase for corrosion resistant problem
It is slightly poor for phosphorus nitrogen compound system.
Therefore, studying by inventor herein, find to introduce the stannic acid that a small amount of high temperature resistant does not separate out in above-mentioned system
Zinc, can not only solve corrosion resistant problem, and and can provides anti-flammability, there is not yet the problem of precipitation.
The molecular formula of zinc stannate is：ZnSnO3, there is very high decomposition temperature, water-soluble low, not migration precipitation.Can be with
Phosphorus constructed of aluminium cooperates with, and improves anti-flammability, and with suppression cigarette effect, reduce smoke density.
Preferably, the average grain diameter D50 of the diethyl hypo-aluminum orthophosphate is 20~50 μm；The aluminium phosphite is averaged
Particle diameter D50 is 20~50 μm；The average grain diameter D50 of the zinc stannate is 20~50 μm.Above-mentioned each powder material is using identical
Particle size range, be easy to several powders uniformly to mix.
The invention also discloses a kind of halogen-free flame-retardant glass fiber to strengthen nylon material, is hindered using the not nitrogenous Halogen of above-mentioned composition
Fire compound system.
Preferably, described halogen-free flame-retardant glass fiber enhancing nylon material, by weight percentage, raw material composition includes：
Described nylon is selected from least one of nylon 6, nylon66 fiber, nylon MXD 6, nylon 6T.
Described auxiliary agent includes lubricant and antioxidant.
Described not nitrogenous halogen-free flameproof compound system is the composite flame retardant system based on phosphorus aluminium, is to confer to fiberglass reinforced Buddhist nun
The functional aid of imperial fire resistance, to reach related standard requirement, its account for whole material system percentage by weight for 10~
30%.
Further preferably, in halogen-free flame-retardant glass fiber enhancing nylon material, described not nitrogenous halogen-free flameproof compound system, press
Percentage by weight meter, raw material composition include：
Diethyl hypo-aluminum orthophosphate 75~90%；
Aluminium phosphite 15~20%；
Zinc stannate 5~10%.
Described not nitrogenous halogen-free flameproof compound system accounts for the weight percent of halogen-free flame-retardant glass fiber enhancing nylon material system
Than for 20~30%.
The halogen-free flame-retardant glass fiber being prepared by above-mentioned formula strengthens nylon material, and it is fire-retardant to can reach UL94V0 (1.6mm)
Grade, and with not etching apparatus, without separating out the advantages of.
The invention also discloses the preparation method of halogen-free flame-retardant glass fiber enhancing nylon material, it is specially：
(1) each component in halogen-free flameproof compound system is weighed by proportioning, and is mixed with each auxiliary agent after high-speed stirred
It is even, obtain powder material；
(2) use double screw extruder, after the temperature stabilization of Dai Ge areas setting, nylon is added from hopper, glass passes through
Glass fiber opening is added to add, the powder material of step (1) is fed by powder charging aperture, starts main frame and feeding machine, extruded, granulation
Described halogen-free flame-retardant glass fiber enhancing nylon material is obtained afterwards.
Compared with prior art, the invention has the advantages that：
Not nitrogenous Halogen resistance provided by the invention based on diethyl hypo-aluminum orthophosphate, aluminium phosphite and zinc stannate compounding composition
Combustion compound system has the advantages that high fire-retardance, non-migratory, not etching apparatus；Glass fiber reinforced nylon material body can be well adapted for
System, the halogen-free flame-retardant glass fiber enhancing nylon material being prepared, can reach UL94V0 (1.6mm) flame retardant rating, and without separating out, no
Etching apparatus.
Embodiment
Embodiment 1
Halogen-free flameproof compound system is applied in glass fiber enhanced nylon, follows these steps and method of testing investigates fire retardant
Performance.
(1) mixture of not nitrogenous halogen-free flame-retardant system
Stirred in height and the compounding flame retardant each component weighed up in advance by proportioning and other auxiliary agents are added in machine, start high-speed stirring
Mix, stir 10min, complete the mixture of powder, discharging.
(2) extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature, after temperature stabilization 20min, Buddhist nun is added from hopper
Dragon, by adding glass fiber opening to add, the powder of step (1) mixture is fed glass by powder charging aperture, starts main frame and feeding machine,
Complete the extruding pelletization of material.The material for having made grain is sent into feed bin by blast system, and dries.
(3) application of material and test
The material dried is molded by injection machine the standard specimen of various testing standard defineds, and carries out correlation
The test of material property.It is primarily upon following performance indications：
Fire-retardant experiment
According to the test of UL94V0 testing standards.
Resistance to migration experiment
The halogen-free flame-retardant glass fiber prepared is strengthened into nylon sample, is put into climatic chamber, 85 DEG C of temperature is set, relatively
Humidity 85%, the state of specimen surface of the visual observations after 168 hours.
Corrosion experiment
One metal derby is set on die head, and high-temperature material passes through 25Kg material granulations in die head and metal block contact, test
The waste of metal afterwards, loss is higher, and corrosion resistance is poorer.If etching extent<0.1% is thought that corrosion is acceptable.
Each material and proportioning are shown in Table 1 in the present embodiment, and resulting testing of materials the results are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, in addition to the ratio of aluminium phosphite and zinc stannate adjusts, keeps flame-retardant system total amount
It is constant.Other materials and proportioning are shown in Table 1, and resulting material the results are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, in addition to the ratio of diethyl hypo-aluminum orthophosphate and aluminium phosphite adjusts, keeps fire-retardant
System total amount is constant.Other materials and proportioning are shown in Table 1, and resulting material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, in addition to without using zinc stannate.Other materials and proportioning are shown in Table 1, resulting
Material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, in addition to without using aluminium phosphite.Other materials and proportioning are shown in Table 1, resulting
Material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, in addition to only using diethyl hypo-aluminum orthophosphate.Other materials and proportioning are shown in Table 1,
Resulting material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, in addition to being compounded using diethyl hypo-aluminum orthophosphate with melamine polyphosphate.
Other materials and proportioning are shown in Table 1, and resulting material the results are shown in Table 1.
Table 1
Claims (9)
- A kind of 1. not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon, it is characterised in that by weight percentage, raw material Composition includes：Diethyl hypo-aluminum orthophosphate 60~90%；Aluminium phosphite 9~30%；Zinc stannate 1~10%.
- 2. the not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon according to claim 1, it is characterised in that described The average grain diameter D50 of diethyl hypo-aluminum orthophosphate is 20~50 μm.
- 3. the not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon according to claim 1, it is characterised in that described The average grain diameter D50 of aluminium phosphite is 20~50 μm.
- 4. the not nitrogenous halogen-free flameproof compound system of glass fiber enhanced nylon according to claim 1, it is characterised in that described The average grain diameter D50 of zinc stannate is 20~50 μm.
- 5. a kind of halogen-free flame-retardant glass fiber strengthens nylon material, it is characterised in that uses according to Claims 1 to 4 is any Not nitrogenous halogen-free flameproof compound system.
- 6. halogen-free flame-retardant glass fiber according to claim 5 strengthens nylon material, it is characterised in that by weight percentage, Raw material composition includes：
- 7. halogen-free flame-retardant glass fiber according to claim 5 strengthens nylon material, it is characterised in that by weight percentage, The raw material composition of the not nitrogenous halogen-free flameproof compound system includes：Diethyl hypo-aluminum orthophosphate 75~80%；Aluminium phosphite 15~20%；Zinc stannate 5~10%.
- 8. halogen-free flame-retardant glass fiber according to claim 5 strengthens nylon material, it is characterised in that described nylon is selected from Buddhist nun At least one of dragon 6, nylon66 fiber, nylon MXD 6, nylon 6T.
- 9. halogen-free flame-retardant glass fiber according to claim 5 strengthens nylon material, it is characterised in that described auxiliary agent includes profit Lubrication prescription and antioxidant.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108795039A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application that dialkyl dithio hypophosphites is cooperateed with organic phosphite |
| CN108997612A (en) * | 2018-08-09 | 2018-12-14 | 江苏利思德新材料有限公司 | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic phosphorous acid metal salt |
| CN109082115A (en) * | 2018-08-09 | 2018-12-25 | 江苏利思德新材料有限公司 | Thermoplastic polymer or the high-temperature thermal stability method of its compound are improved using inorganic phosphorous acid metal salt |
| CN109181293A (en) * | 2018-08-09 | 2019-01-11 | 浙江大学 | Melamine derivative based flame retardant high-temperature thermal stability method and products thereof and application are improved using inorganic and alkyl phosphorous acid metal salt |
| CN111171562A (en) * | 2020-02-18 | 2020-05-19 | 江苏博云塑业股份有限公司 | Halogen-free flame-retardant glass fiber reinforced nylon material and preparation method thereof |
| CN113549321A (en) * | 2021-07-22 | 2021-10-26 | 中广核俊尔(浙江)新材料有限公司 | Black phosphorus flame-retardant polyamide composite material capable of achieving high-definition laser marking and resisting wet-heat precipitation and preparation method thereof |
| EP4215575A4 (en) * | 2020-10-12 | 2024-03-13 | Jiangsu Liside New Material Co., Ltd. | Halogen-free flame-retardant compounded system having resistance to high heat and high shear and high flame resistance, and application thereof |
| CN118222086A (en) * | 2023-10-19 | 2024-06-21 | 诺为新材料(杭州)有限责任公司 | Precipitation-resistant halogen-free flame-retardant polyamide composition and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108795039A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | The halogen-free flame-retardant system and its application that dialkyl dithio hypophosphites is cooperateed with organic phosphite |
| CN108997612A (en) * | 2018-08-09 | 2018-12-14 | 江苏利思德新材料有限公司 | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic phosphorous acid metal salt |
| CN109082115A (en) * | 2018-08-09 | 2018-12-25 | 江苏利思德新材料有限公司 | Thermoplastic polymer or the high-temperature thermal stability method of its compound are improved using inorganic phosphorous acid metal salt |
| CN109181293A (en) * | 2018-08-09 | 2019-01-11 | 浙江大学 | Melamine derivative based flame retardant high-temperature thermal stability method and products thereof and application are improved using inorganic and alkyl phosphorous acid metal salt |
| CN110054807A (en) * | 2018-08-09 | 2019-07-26 | 江苏利思德新材料有限公司 | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using inorganic phosphorous acid metal salt |
| CN110054807B (en) * | 2018-08-09 | 2021-02-02 | 江苏利思德新材料有限公司 | Phosphorus-nitrogen halogen-free flame retardant composition for improving thermal stability by using inorganic metal phosphite and application thereof |
| CN109181293B (en) * | 2018-08-09 | 2021-03-05 | 浙江大学 | Method for improving high-temperature thermal stability of melamine derivative flame retardant by using inorganic and alkyl phosphite metal salt, product and application thereof |
| CN111171562A (en) * | 2020-02-18 | 2020-05-19 | 江苏博云塑业股份有限公司 | Halogen-free flame-retardant glass fiber reinforced nylon material and preparation method thereof |
| EP4215575A4 (en) * | 2020-10-12 | 2024-03-13 | Jiangsu Liside New Material Co., Ltd. | Halogen-free flame-retardant compounded system having resistance to high heat and high shear and high flame resistance, and application thereof |
| CN113549321A (en) * | 2021-07-22 | 2021-10-26 | 中广核俊尔(浙江)新材料有限公司 | Black phosphorus flame-retardant polyamide composite material capable of achieving high-definition laser marking and resisting wet-heat precipitation and preparation method thereof |
| CN118222086A (en) * | 2023-10-19 | 2024-06-21 | 诺为新材料(杭州)有限责任公司 | Precipitation-resistant halogen-free flame-retardant polyamide composition and preparation method thereof |
| CN118222086B (en) * | 2023-10-19 | 2024-10-18 | 诺为新材料(杭州)有限责任公司 | Precipitation-resistant halogen-free flame-retardant polyamide composition and preparation method thereof |
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