CN109111711A - A kind of polycarbonate compositions and the preparation method and application thereof - Google Patents
A kind of polycarbonate compositions and the preparation method and application thereof Download PDFInfo
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- CN109111711A CN109111711A CN201810764488.3A CN201810764488A CN109111711A CN 109111711 A CN109111711 A CN 109111711A CN 201810764488 A CN201810764488 A CN 201810764488A CN 109111711 A CN109111711 A CN 109111711A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a kind of polycarbonate compositions, by weight, including consisting of: 0.5-98.5 parts of a, polycarbonate；B, sulfonate salt flame 0.15-0.95 parts；C, synergistic flame retardant 0.03-0.72 parts；D, siloxanes 0.04-1.1 parts；E, anti-dripping agent 0.02-1 parts.The present invention, which is selected, adds certain content and particular kind of anti-dripping agent in polycarbonate compositions formula, with polycarbonate, sulfonate salt flame, synergistic flame retardant and the siloxanes of certain content, good fire-retardant and anti-dripping effects can be realized under lower burning melt viscosity, the polycarbonate compositions still have good flame retardant property and thermal stability and molded appearance in the fire-retardant film with a thickness of 0.40mm.
Description
Technical field
The present invention relates to engineering plastics technical field, in particular to a kind of polycarbonate compositions and the preparation method and application thereof.
Background technique
Polycarbonate (PC) has mechanical performance, dimensional stability and the heat resistance of aggregative equilibrium, especially with excellent
Impact strength and creep resistant title.For the visible light transmittance of PC resin 90% or more, thermal decomposition temperature is high, has excellent
Good electrical insulating property is widely used in many necks such as machinery, automobile, space flight and aviation, building, electric, office and household supplies
Domain is especially used widely in the polycarbonate insulating film of electric application.
The polycarbonate insulating film of electric application, thickness level are lower than 0.5mm, can be divided into non-flame resistant class and resistance
Type is fired, the insulating film of flame retardant type is application development trend, and as materials of electronic components, material is thinning development and safety
Performance guarantee needs to have stable anti-flammability in reduced thickness, to reduce the pyrolytic damage issued by electronic component, thus
Also need to guarantee high heat resistance and storage stability.Simultaneously also to its folding property, proof voltage and heat resistance are to be expected
's.Although many polycarbonate compositions can provide the beneficial combination of above-mentioned performance, there has been no very thin polycarbonate
Material realizes the desired anti-fire performance in the relevant report for requiring the performance in harsh electric insulation application.With electricity
The product & product design that becomes to disappear fastly of sub- equipment is thinning trend, and insulating film increases estimated about 20% annual, and lightening, function
Change, the development trend of environmental protection certainly will promote halogen-free flame retardant polycarbonate film material to become new in electric insulation application
The show risen.
However, sulfonate salt flame can promote PC to be cross-linked into charcoal in PC combustion process, to improve the anti-flammability of PC
Can, but the saturation additive amount of sulfonate is low, and PC is instead resulted in when being excessively used and is seriously degraded, and causes mechanical property and flame retardant property bad
Change.In order to obtain superior flame retardant effect, p-sulfonic acid salt fire retardant is needed to carry out compounding synergistic, such as Chinese patent
CN201510443170.Mineral filler is common fire-retardant synergistic component, but its surface is generally in alkalinity, and having causes PC matrix to drop
The risk of solution, the application in PC fire-retardant combination are restricted.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that one kind is provided can be compared with low burn
It burns and realizes good fire-retardant and anti-dripping effects under melt viscosity, and still have in the fire-retardant film with a thickness of 0.40mm
The polycarbonate compositions of good flame retardant property and thermal stability and molded appearance.
It is a further object of the present invention to provide the preparation methods of above-mentioned polycarbonate compositions.
Another object of the present invention is to provide the purposes of above-mentioned polycarbonate compositions.
The present invention is achieved by the following technical solutions:
A kind of polycarbonate compositions, by weight, including consisting of:
A, polycarbonate 0.5-98.5 parts；
B, sulfonate salt flame 0.15-0.95 parts；
C, synergistic flame retardant 0.03-0.72 parts；
D, siloxanes 0.04-1.1 parts；
E, anti-dripping agent 0.02-1 parts.
Wherein, the viscosity average molecular weigh of the polycarbonate is 18000-50000.Wherein, viscosity average molecular weigh be by using
Methylene chloride is calculated as solvent in the solution viscosity that test temperature is 25 DEG C.
Wherein, the sulfonate salt flame is selected from perfluoro alkyl sulfonic acid potassium, benzenesulfonyl benzene sulfonyl potassium, paratoluenesulfonic acid sodium salt
One or more of, preferably perfluorobutyl potassium sulfonate.
Wherein, the viscosity at the synergistic flame retardant is 140 DEG C in fusing point is 80mPa s-9000mPa s, acid value 6-
90；Selected from one or more of polyolefin epoxide, maleic anhydride modified polyolefin, esters of acrylic acid, preferably maleic acid
Anhydride modified polyolefin.
Wherein, the siloxanes is selected from poly- aminopropyl phenyl silsesquioxane, terminal hydroxy group polyaminopropylsilsesquioxane, gathers
One of methyl silsesquioxane, polyphenylsilsesquioxane, dimethyl silicone polymer, polymethylphenylsiloxane are several
Kind, preferably polyphenylsilsesquioxane.
Wherein, the anti-dripping agent is selected from polytetrafluoroethylene (PTFE), the polytetrafluoroethylene (PTFE) that silicone coats, coated with silica poly- four
One of polytetrafluoroethylene (PTFE) that vinyl fluoride, the polytetrafluoroethylene (PTFE) of methacrylate polymers cladding, acrylonitrile coat is several
Kind；The preferably polytetrafluoroethylene (PTFE) of silicone cladding；More preferably viscosity is 15cps -50cps at 25 DEG C, and polytetrafluoroethyl-ne
The polytetrafluoroethylene (PTFE) that the silicone that the molecular weight of alkene is 300000-800000 coats.
Wherein, the weight additive amount of the siloxanes is 0.56-1.53 times of the weight additive amount of synergistic flame retardant, preferably
0.75-1.25 times；The weight additive amount of the anti-dripping agent is 0.07-1.67 times of the weight additive amount of synergistic flame retardant, excellent
Select 0.5-1.0 times.
Polycarbonate compositions of the present invention can also include by weight 0-24 parts of mineral fillers, 0-1 parts
Antioxidant and 0-1 parts of lubricants；Wherein, the mineral filler is in talcum powder, titanium dioxide, mica, montmorillonite, kaolin
It is one or more of.
In addition, including the following steps: the invention also discloses the preparation method of above-mentioned polycarbonate compositions
Each component is uniform in high-speed mixer and mixing in proportion, it is added in double screw extruder, in 240 DEG C -260 DEG C of temperature
Then lower carry out melting mixing is granulated, is cooling, being dried to obtain polycarbonate compositions.
The invention also discloses application of the above-mentioned polycarbonate compositions in the insulation film of electronic and electrical field.
Compared with prior art, the present invention having the following beneficial effects:
The present invention, which selects in polycarbonate compositions formula, adds certain content and particular kind of anti-dripping agent and specific
Polycarbonate, sulfonate salt flame, synergistic flame retardant and the siloxanes of content can be realized good under lower burning melt viscosity
Good fire-retardant and anti-dripping effects, the polycarbonate compositions still have good in the fire-retardant film with a thickness of 0.40mm
Flame retardant property and thermal stability and molded appearance.
Specific embodiment
Further illustrate that the present invention, following embodiment are the preferable embodiment party of the present invention below by specific embodiment
Formula, but embodiments of the present invention are not limited by following embodiments.
The testing standard or method of each performance:
It burns the test method of melt index (MI): testing standard ASTM D1238,300 DEG C, 1.2 kg；The definition for melt viscosity of burning
Are as follows: in combustion, in the case that batten receives the identical combustion heat, the viscosity size of the melt generated inside carbon-coating,
Its medium viscosity is excessive, can cause into that charcoal rate is not high and burning time is too long leads to test crash, and viscosity is too small to will lead to carbon-coating
Drippage caused by rupture is just able to achieve stable fire-retardant stabilization to test crash, melt viscosity needs in appropriate range
Property, wherein the fire-retardant stability of V-0 judges that wherein A grade represents 10 by the burning time and combustion state of 10 battens
The burning time of middle t1 is less than 3s, and the burning average time of t2 is respectively less than 3s, and single total burn time is no more than 7s, and does not have
It drips；The burning time that B rank represents 10 middle t1 is less than 5s, and the burning time of t2,10 battens burnt without limitation
Total time does not drip no more than 50s；The burning time that C rank represents 10 middle t1 is less than 5s, and the t2 time is not
It limits, 10 batten total burn times no more than 50s, occur dripping but not ignite；
The test method of flame retardant rating (0.40mm): being prepared into 0.40mm film for polycarbonate compositions, test flame retardant rating,
Testing standard is UL94；
The test method of room temperature notch impact strength: testing standard ASTM D256；
The test method of bending strength: testing standard ASTM D790；
The test method of tensile strength: testing standard ASTM D638；
The test method of thermal stability: TGA initial pyrolyzation temperature is used to characterize: with rate of weight loss in TGA curve for 5%
When corresponding temperature as initial pyrolyzation temperature；TGA temperature of initial decomposition is higher, and the thermal stability of material is better；
The test method of appearance ratings: material is cast into 0.40mm-0.45mm thickness thin film, according to 523 standard of ASTM D
Measure the surface gloss under 60 ° of angles.Test result is greater than 30 and is defined as " 1 grade ", and when test result 30-15 is defined as 2 grades,
3 grades are defined as when test result is less than 15.
Now raw material used in embodiment and comparative example are done as described below, but are not limited to these materials:
Polycarbonate used in the present invention:
PC-1, viscosity average molecular weigh 25000；
PC-2, viscosity average molecular weigh 45000；
Synergistic flame retardant used in the present invention:
Maleic anhydride modified polyolefin, the viscosity at being 140 DEG C in fusing point are 150 mPa s, acid value 60；
Oxidized polyolefin, the viscosity at being 140 DEG C in fusing point are 8500 mPa s, acid value 16；
Siloxanes used in the present invention:
Polyphenylsilsesquioxane, trade names KR-2710；
Terminal hydroxy group polyaminopropylsilsesquioxane, trade names FCA-107；
Anti-dripping agent used in the present invention:
Anti-dripping agent -1: viscosity is 40 cps, and the molecular weight of polytetrafluoroethylene (PTFE) is 500000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -2: viscosity 15cps, the molecular weight of polytetrafluoroethylene (PTFE) are 800000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -3: viscosity is 50 cps, and the molecular weight of polytetrafluoroethylene (PTFE) is 300000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -4: viscosity 5cps, the molecular weight of polytetrafluoroethylene (PTFE) are 500000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -5: viscosity 80cps, the molecular weight of polytetrafluoroethylene (PTFE) are 500000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -6: viscosity 40cps, the molecular weight of polytetrafluoroethylene (PTFE) are 100000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -7: viscosity 40cps, the molecular weight of polytetrafluoroethylene (PTFE) are 1000000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -8: viscosity 5cps, the molecular weight of polytetrafluoroethylene (PTFE) are 1000000, the polytetrafluoroethylene (PTFE) of silicone cladding；
Anti-dripping agent -9: viscosity 40cps, the molecular weight of polytetrafluoroethylene (PTFE) are 500000, methacrylate polymers cladding
Polytetrafluoroethylene (PTFE)；
Sulfonate salt flame used in the present invention: perfluorobutyl potassium sulfonate；
Mineral filler used in the present invention: talcum powder, mesh number are 3000 mesh；
Antioxidant used in the present invention: Hinered phenols antioxidant CHINOX 1076 and mercaptan kind antioxidant JADEWIN AN
The compounding of 412S, and the compounding of the two compares for 1:1；
Lubricant used in the present invention: pentaerythritol stearate series lubricant agent LOXIOL P 861/3.5, German Corning.
Embodiment 1-17 and comparative example 1-8: the preparation of polycarbonate compositions
It is by the proportion of table 1 that each component is uniform in high-speed mixer and mixing, it is added in double screw extruder, at 240 DEG C -260 DEG C
At a temperature of carry out melting mixing, be then granulated, be cooling, being dried to obtain polycarbonate compositions；To polycarbonate compositions
Burning melt viscosity, fire-retardant thickness, melt index, flame retardant rating (0.40 mm), room temperature notch impact strength, bending strength, drawing
It stretches the performance indicators such as intensity, thermal stability and appearance ratings to be tested, test data is as shown in table 1.
Specific proportion (parts by weight) and its test performance result of table 1 embodiment 1-17 and comparative example 1-8
Continued 1
Continued 1
。
Claims (10)
1. a kind of polycarbonate compositions, by weight, including consisting of:
A, polycarbonate 0.5-98.5 parts；
B, sulfonate salt flame 0.15-0.95 parts；
C, synergistic flame retardant 0.03-0.72 parts；
D, siloxanes 0.04-1.1 parts；
E, anti-dripping agent 0.02-1 parts.
2. polycarbonate compositions according to claim 1, which is characterized in that the viscosity average molecular weigh of the polycarbonate is
18000-50000。
3. polycarbonate compositions according to claim 1, which is characterized in that the sulfonate salt flame is selected from perfluor alkane
One or more of base potassium sulfonate, benzenesulfonyl benzene sulfonyl potassium, paratoluenesulfonic acid sodium salt, preferably perfluorobutyl potassium sulfonate.
4. polycarbonate compositions according to claim 1, which is characterized in that the synergistic flame retardant is 140 in fusing point
Viscosity at DEG C is 80mPa s-9000mPa s, acid value 6-90；Selected from polyolefin epoxide, maleic anhydride modified polyolefin,
One or more of esters of acrylic acid, preferably maleic anhydride modified polyolefin.
5. polycarbonate compositions according to claim 1, which is characterized in that the siloxanes is selected from poly- aminopropyl phenyl
Silsesquioxane, terminal hydroxy group polyaminopropylsilsesquioxane, poly methyl silsesquioxane, polyphenylsilsesquioxane, poly- diformazan
One or more of radical siloxane, polymethylphenylsiloxane, preferably polyphenylsilsesquioxane.
6. polycarbonate compositions according to claim 1, which is characterized in that the anti-dripping agent is selected from polytetrafluoroethyl-ne
The polytetrafluoro that alkene, the polytetrafluoroethylene (PTFE) of silicone cladding, coated with silica polytetrafluoroethylene (PTFE), methacrylate polymers coat
One or more of ethylene, polytetrafluoroethylene (PTFE) of acrylonitrile cladding；The preferably polytetrafluoroethylene (PTFE) of silicone cladding；More preferably
It is 15 cps -50 cps at 25 DEG C for viscosity, and the silicone that the molecular weight of polytetrafluoroethylene (PTFE) is 300000-800000 coats
Polytetrafluoroethylene (PTFE).
7. polycarbonate compositions according to claim 1, which is characterized in that the weight additive amount of the siloxanes is association
Imitate 0.56-1.53 times, preferably 0.75-1.25 times of the weight additive amount of fire retardant；The weight additive amount of the anti-dripping agent is
0.07-1.67 times of the weight additive amount of synergistic flame retardant, preferably 0.5-1.0 times.
8. polycarbonate compositions according to claim 1, which is characterized in that further include 0-24 parts of mines by weight
Object filler, 0-1 part antioxidant and 0-1 parts of lubricants；Wherein, it is de- to be selected from talcum powder, titanium dioxide, mica, illiteracy for the mineral filler
One or more of soil, kaolin.
9. a kind of preparation method of such as described in any item polycarbonate compositions of claim 1-8, includes the following steps:
Each component is uniform in high-speed mixer and mixing in proportion, it is added in double screw extruder, in 240 DEG C -260 DEG C of temperature
Then lower carry out melting mixing is granulated, is cooling, being dried to obtain polycarbonate compositions.
10. such as the described in any item polycarbonate compositions of claim 1-8 answering in the insulation film of electronic and electrical field
With.
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| CN201810764488.3A CN109111711A (en) | 2018-07-12 | 2018-07-12 | A kind of polycarbonate compositions and the preparation method and application thereof |
| PCT/CN2019/094312 WO2020011058A1 (en) | 2018-07-12 | 2019-07-02 | Polycarbonate composition and preparation method therefor and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020011058A1 (en) * | 2018-07-12 | 2020-01-16 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor and application thereof |
| CN114854187A (en) * | 2022-04-01 | 2022-08-05 | 万华化学集团股份有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN116285332A (en) * | 2023-03-14 | 2023-06-23 | 金发科技股份有限公司 | Heat-conducting glass fiber reinforced nylon material and preparation method and application thereof |
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| CN108314888A (en) * | 2018-01-30 | 2018-07-24 | 金发科技股份有限公司 | A kind of polycarbonate compositions and application |
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| CN104945881A (en) * | 2015-07-24 | 2015-09-30 | 广州市聚赛龙工程塑料有限公司 | Thin film level halogen-free flame retardant polycarbonate material, preparation method and application thereof |
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| WO2020011058A1 (en) * | 2018-07-12 | 2020-01-16 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor and application thereof |
| CN114854187A (en) * | 2022-04-01 | 2022-08-05 | 万华化学集团股份有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN114854187B (en) * | 2022-04-01 | 2023-10-20 | 万华化学集团股份有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN116285332A (en) * | 2023-03-14 | 2023-06-23 | 金发科技股份有限公司 | Heat-conducting glass fiber reinforced nylon material and preparation method and application thereof |
| CN116285332B (en) * | 2023-03-14 | 2024-05-07 | 金发科技股份有限公司 | Heat-conducting glass fiber reinforced nylon material and preparation method and application thereof |
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| WO2020011058A1 (en) | 2020-01-16 |
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