CN104861620A - Halogen-free flame-retardant enhanced PC/PBT alloy and preparation method therefor - Google Patents

Halogen-free flame-retardant enhanced PC/PBT alloy and preparation method therefor Download PDF

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Publication number
CN104861620A
CN104861620A CN201410685607.8A CN201410685607A CN104861620A CN 104861620 A CN104861620 A CN 104861620A CN 201410685607 A CN201410685607 A CN 201410685607A CN 104861620 A CN104861620 A CN 104861620A
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halogen
pbt
free
strengthens
pbt alloy
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不公告发明人
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Qingdao Tongchuang Energy Saving Environmental Protection Engineering Co Ltd
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Qingdao Tongchuang Energy Saving Environmental Protection Engineering Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08K2201/004—Additives being defined by their length
    • 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
    • C08L2201/22—Halogen free composition
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a halogen-free flame-retardant enhanced PC/PBT alloy and a preparation method therefor. The enhanced PC/PBT alloy comprises the following ingredients, by weight, 30%-60% of PC, 20%-30% PBT, 1%-4% of compatilizers, 0.1%-1% of triphenyl phosphate, 3%-12% of halogen-free flame retardant master batch, 8%-15% of glass fibers, 4%-8% of flexibilizers, 0.1%-0.5% of anti-oxidants and 0.1%-1% of lubricants. The beneficial effects are that the enhanced PC/PBT alloy has excellent shock resistance of PC and good chemical resistance of PBT, has excellent impact resistance and keeps high mechanical strength; the flame retardant performance is good, the requirements of halogen-free, low-smoke, high efficiency and UL94V-0 level flame retardation performance are met, and therefore the application effects of the PC/PBT alloy are raised greatly and the application fields are widened greatly.

Description

Halogen-free flameproof strengthens PC/PBT Alloy And Preparation Method
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of halogen-free flameproof strengthens PC/PBT Alloy And Preparation Method.
Background technology
PC/PBT(polycarbonate/polybutylene terephthalate) alloy material has the advantages such as high thermotolerance, good impact property and excellent chemical resistant properties, at present in a lot of fields in be widely used.But the PC/PBT of non-modified exists, and consistency is bad, the problem of poor fire, this will strongly limit its range of application.
Summary of the invention
The object of the present invention is to provide that a kind of mechanical property is good, the halogen-free flameproof of excellent fireproof performance strengthens PC/PBT Alloy And Preparation Method.
The technical solution adopted for the present invention to solve the technical problems is: halogen-free flameproof strengthens PC/PBT alloy, and its component by mass percent proportioning is: PC 30% ~ 60%, PBT 20% ~ 30%, compatilizer 1% ~ 4%, triphenyl phosphite 0.1% ~ 1%, halogen-free flame-retardant master batch 3% ~ 12%, glass fibre 8% ~ 15%, toughner 4% ~ 8%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.
Described PC is bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 20000 ~ 30000g/mol.
Described PBT is polybutylene terephthalate, and its intrinsic viscosity is 0.8 ~ 1.5dL/g.
Described compatilizer is glycidyl methacrylate-styrene-acrylonitrile terpolymer GMA-St-AN, and glycidyl methacrylate accounts for 1 wt% ~ 5 wt%, vinyl cyanide accounts for 27 wt% ~ 30 wt%.
Described halogen-free flame-retardant master batch is made up of PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% and obtained halogen-free flame-retardant master batch.
Described glass fibre be surface through silane coupler modified process and diameter at 8 ~ 12 μm, the alkali free glass fibre of length within the scope of 3 ~ 6mm.
Described toughner is the one in styrene-butadiene-styrene block copolymer SBS, MBS terpolymer MBS, Methylacrylate-Acrylate Copolymer ACR, thermoplastic polyester elastomer TPEE, polyolefin elastomer.
Described oxidation inhibitor is the one in the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168.
Described lubricant is pentaerythritol stearate or modification ethylene bis-fatty acid amides.
Above-mentioned halogen-free flameproof strengthens the preparation method of PC/PBT alloy, comprises the following steps:
(1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PBT at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by;
(2), halogen-free flame-retardant master batch is prepared: PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% will be taken by weight ratio, add after stirring in super mixer, discharging add in twin screw extruder melt extrude, cooling granulation and dry after obtained halogen-free phosphorus-free inflaming retarding master batch, stand-by;
(3), add in high-speed mixer by taking dry PC and PBT by weight ratio, add compatilizer, triphenyl phosphite, toughner, oxidation inhibitor, lubricant by weight ratio simultaneously, and add the obtained halogen-free flame-retardant master batch of step (2) by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing;
(4), the compound of step (3) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 600r/min, processing temperature is 210 DEG C ~ 260 DEG C scopes, then extruding pelletization, obtains halogen-free flameproof of the present invention and strengthens PC/PBT alloy.
The invention has the beneficial effects as follows, the present invention is while the good chemical resistance of the excellent impact resistance energy and PBT with PC, also there is excellent shock resistance and keep higher mechanical strength, and flame retardant properties is good, meet the flame-retardancy requirements of Halogen, low cigarette, efficient and UL94 V-0 level, thus greatly improve effect and the Application Areas of PC/PBT alloy.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with concrete preferred embodiment.
Embodiment 1:
A kind of halogen-free flameproof strengthens PC/PBT alloy, its component by mass percent proportioning is: PC 41%, PBT 20%, compatilizer 2.5%, triphenyl phosphite 0.5%, halogen-free flame-retardant master batch 12%, glass fibre 15%, MBS 8%, antioxidant 1010 0.2%, modification ethylene bis-fatty acid amides 0.8%, the weight-average molecular weight of described PC is 20000 ~ 30000g/mol, and the intrinsic viscosity of described PBT is 0.8 ~ 1.5dL/g; Described compatilizer is glycidyl methacrylate-styrene-acrylonitrile terpolymer GMA-St-AN, and glycidyl methacrylate accounts for 1 wt% ~ 5 wt%, vinyl cyanide accounts for 27 wt% ~ 30 wt%; Described halogen-free flame-retardant master batch is made up of PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% and obtained halogen-free flame-retardant master batch; Described glass fibre be surface through silane coupler modified process and diameter at 8 ~ 12 μm, the alkali free glass fibre of length within the scope of 3 ~ 6mm.
Preparation method: (1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PBT at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by; (2), halogen-free flame-retardant master batch is prepared: PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% will be taken by weight ratio, add after stirring in super mixer, discharging add in twin screw extruder melt extrude, cooling granulation and dry after obtained halogen-free phosphorus-free inflaming retarding master batch, stand-by; (3), add in high-speed mixer by taking dry PC and PBT by weight ratio, add compatilizer, triphenyl phosphite, MBS, antioxidant 1010, modification ethylene bis-fatty acid amides by weight ratio simultaneously, and add the obtained halogen-free flame-retardant master batch of step (2) by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing; (4), the compound of step (3) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 600r/min, processing temperature is 210 DEG C ~ 260 DEG C scopes, then extruding pelletization, obtains halogen-free flameproof of the present invention and strengthens PC/PBT alloy.
Embodiment 2:
A kind of halogen-free flameproof strengthens PC/PBT alloy, its component by mass percent proportioning is: the compound 0.2% of PC 42%, PBT 30%, compatilizer 4%, triphenyl phosphite 1%, halogen-free flame-retardant master batch 8%, glass fibre 8%, TPEE 6%, antioxidant 1076 and irgasfos 168, modification ethylene bis-fatty acid amides 0.8%, the weight-average molecular weight of described PC is 20000 ~ 30000g/mol, and the intrinsic viscosity of described PBT is 0.8 ~ 1.5dL/g; Described compatilizer is glycidyl methacrylate-styrene-acrylonitrile terpolymer GMA-St-AN, and glycidyl methacrylate accounts for 1 wt% ~ 5 wt%, vinyl cyanide accounts for 27 wt% ~ 30 wt%; Described halogen-free flame-retardant master batch is made up of PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% and obtained halogen-free flame-retardant master batch; Described glass fibre be surface through silane coupler modified process and diameter at 8 ~ 12 μm, the alkali free glass fibre of length within the scope of 3 ~ 6mm.
Preparation method: (1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PBT at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by; (2), halogen-free flame-retardant master batch is prepared: PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% will be taken by weight ratio, add after stirring in super mixer, discharging add in twin screw extruder melt extrude, cooling granulation and dry after obtained halogen-free phosphorus-free inflaming retarding master batch, stand-by; (3), add in high-speed mixer by taking dry PC and PBT by weight ratio, add compound, the modification ethylene bis-fatty acid amides of compatilizer, triphenyl phosphite, TPEE, antioxidant 1076 and irgasfos 168 by weight ratio simultaneously, and add the obtained halogen-free flame-retardant master batch of step (2) by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing; (4), the compound of step (3) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 600r/min, processing temperature is 210 DEG C ~ 260 DEG C scopes, then extruding pelletization, obtains halogen-free flameproof of the present invention and strengthens PC/PBT alloy.

Claims (8)

1. a halogen-free flameproof strengthens PC/PBT alloy, it is characterized in that, its component by mass percent proportioning is: PC 30% ~ 60%, PBT 20% ~ 30%, compatilizer 1% ~ 4%, triphenyl phosphite 0.1% ~ 1%, halogen-free flame-retardant master batch 3% ~ 12%, glass fibre 8% ~ 15%, toughner 4% ~ 8%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.
2. halogen-free flameproof according to claim 1 strengthens PC/PBT alloy, it is characterized in that, described compatilizer is glycidyl methacrylate-styrene-acrylonitrile terpolymer GMA-St-AN, and glycidyl methacrylate accounts for 1 wt% ~ 5 wt%, vinyl cyanide accounts for 27 wt% ~ 30 wt%.
3. halogen-free flameproof according to claim 1 strengthens PC/PBT alloy; it is characterized in that, described halogen-free flame-retardant master batch is made up of PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% and obtained halogen-free flame-retardant master batch.
4. halogen-free flameproof according to claim 1 strengthens PC/PBT alloy, it is characterized in that, described glass fibre be surface through silane coupler modified process and diameter at 8 ~ 12 μm, the alkali free glass fibre of length within the scope of 3 ~ 6mm.
5. halogen-free flameproof according to claim 1 strengthens PC/PBT alloy, it is characterized in that, described toughner is the one in styrene-butadiene-styrene block copolymer SBS, MBS terpolymer MBS, Methylacrylate-Acrylate Copolymer ACR, thermoplastic polyester elastomer TPEE, polyolefin elastomer.
6. halogen-free flameproof according to claim 1 strengthens PC/PBT alloy, and it is characterized in that, described oxidation inhibitor is the one in the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168.
7. halogen-free flameproof according to claim 1 strengthens PC/PBT alloy, and it is characterized in that, described lubricant is pentaerythritol stearate or modification ethylene bis-fatty acid amides.
8. halogen-free flameproof according to claim 1 strengthens the preparation method of PC/PBT alloy, it is characterized in that, comprises the following steps:
(1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PBT at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by;
(2), halogen-free flame-retardant master batch is prepared: PBT resin 30wt%, polydimethylsiloxane 60wt%, potassium phenylsulphonyl benzene sulfonate 2wt%, tetrafluoroethylene 3wt% and pentaerythritol stearate 5wt% will be taken by weight ratio, add after stirring in super mixer, discharging add in twin screw extruder melt extrude, cooling granulation and dry after obtained halogen-free phosphorus-free inflaming retarding master batch, stand-by;
(3), add in high-speed mixer by taking dry PC and PBT by weight ratio, add compatilizer, triphenyl phosphite, toughner, oxidation inhibitor, lubricant by weight ratio simultaneously, and add the obtained halogen-free flame-retardant master batch of step (2) by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing;
(4), the compound of step (3) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 600r/min, processing temperature is 210 DEG C ~ 260 DEG C scopes, then extruding pelletization, obtains halogen-free flameproof of the present invention and strengthens PC/PBT alloy.
CN201410685607.8A 2014-11-25 2014-11-25 Halogen-free flame-retardant enhanced PC/PBT alloy and preparation method therefor Pending CN104861620A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161180A (en) * 2018-08-02 2019-01-08 广东顺德顺炎新材料股份有限公司 High apparent property glass fiber reinforced PC/PBT alloy vehicle wiper material and preparation
CN109867922A (en) * 2018-12-28 2019-06-11 聚石化学(苏州)有限公司 A kind of and excellent halogen free flame-retardant reinforced PBT composite material and preparation method thereof of adhering with epoxy resin
JP2019210397A (en) * 2018-06-06 2019-12-12 三菱エンジニアリングプラスチックス株式会社 High concentration phosphorus-based flame retardant masterbatch, polycarbonate resin composition, and manufacturing method of masterbatch

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019210397A (en) * 2018-06-06 2019-12-12 三菱エンジニアリングプラスチックス株式会社 High concentration phosphorus-based flame retardant masterbatch, polycarbonate resin composition, and manufacturing method of masterbatch
JP7060452B2 (en) 2018-06-06 2022-04-26 三菱エンジニアリングプラスチックス株式会社 High-concentration phosphorus flame retardant masterbatch, polycarbonate resin composition, and method for manufacturing masterbatch
CN109161180A (en) * 2018-08-02 2019-01-08 广东顺德顺炎新材料股份有限公司 High apparent property glass fiber reinforced PC/PBT alloy vehicle wiper material and preparation
CN109161180B (en) * 2018-08-02 2020-11-20 广东顺德顺炎新材料股份有限公司 High-apparent-performance glass fiber reinforced PC/PBT alloy automobile windscreen wiper material and preparation thereof
CN109867922A (en) * 2018-12-28 2019-06-11 聚石化学(苏州)有限公司 A kind of and excellent halogen free flame-retardant reinforced PBT composite material and preparation method thereof of adhering with epoxy resin

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