CN104693759A - Toughening modification PC/PBT flame-retardant alloy - Google Patents
Toughening modification PC/PBT flame-retardant alloy Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- 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
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- 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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- 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
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- C08J2435/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/06—Copolymers with vinyl aromatic monomers
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- C—CHEMISTRY; METALLURGY
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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Abstract
The invention discloses a toughening modification PC/PBT flame-retardant alloy. The toughening modification PC/PBT flame-retardant alloy comprises the components in percentage by mass: 40-60 percent of PC, 20-40 percent of PBT, 3-8 percent of toughening agents, 5-10 percent of phosphorus based flame retardants, 0.1-1 percent of molten drop, 0.1-1.5 percent of a transesterification inhibitor, 0.5-3 percent of compatilizers, 0.1-0.5 percent of antioxidant, and 0.1-1 percent of a lubricating agent. Compared with the prior art, the toughening modification PC/PBT flame-retardant alloy has the beneficial effects that the PBT flame-retardant masterbatch is prepared at first and is used for modifying PC, a proper amount of the toughening agent, the transesterification inhibitor and the compatilizer are added so that the prepared PC/PBT alloy system has the original excellent performance of the PC and PBT, and is high in flame-retardant performance and anti-impact strength, high in processing fluidity, low in cost and simple in preparation process.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of PC/PBT flame-retardant alloy of toughening modifying.
Background technology
PC/PBT alloy (polycarbonate/polybutylene terephthalate) has that warpage sex change is little, good stability of the dimension, good fluidity, thermal linear expansion coefficient is little, the features such as chemical solvent resistance energy is excellent, a kind of alloy plastic that industrial using value is higher, can be used for manufacturing collision bumper, automobile door handle, body of a motor car side plate, electrically, electronic equipment part etc.But from polymer aggregational state structure, PC is non-crystalline polymer, and PBT is crystalline polymer, therefore PC/PBT belongs to typically noncrystalline with crystallization co-mixing system, the shock strength that its interface compatibility is bad, affect material, and the low performance requriements with high flame retardant can not be met of flame retardant resistance, this will limit its range of application greatly.Therefore, the modification of the aspects such as fire-retardant, enhancing, increase-volume is carried out to PC/PBT alloy necessary.
Summary of the invention
The object of the present invention is to provide a kind of PC/PBT flame-retardant alloy of toughening modifying.
The technical solution adopted for the present invention to solve the technical problems is: a kind of PC/PBT flame-retardant alloy of toughening modifying, and its component by mass percent proportioning is: PC 40% ~ 60%, PBT 20% ~ 40%, toughner 3% ~ 8%, phosphorus flame retardant 5% ~ 10%, anti-molten drop agent 0.1% ~ 1%, ester exchange inhibitor 0.1% ~ 1.5%, compatilizer 0.5% ~ 3%, 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 ~ 40000g/mol.
Described PBT is polybutylene terephthalate.
Described toughner is styrene-butadiene-methyl acrylic ester terpolymers (MBS) or Methylacrylate-Acrylate Copolymer (ACR).
Described phosphorus flame retardant is one or more in triphenylphosphate (TPP), two (diphenyl phosphate) (RDP) of Resorcinol, dihydroxyphenyl propane-bis-(diphenyl phosphate) (BDP), Resorcinol-bis-(2,6-xylyl) phosphoric acid ester (RXP), melamine polyphosphate (MPP).
Described anti-molten drop agent is the compound of polytetrafluoroethylene (PTFE) for mass ratio 1:1 and polyvinylidene difluoride (PVDF) (PVDF).
Described ester exchange inhibitor is triphenyl phosphite (TPPi) or Sodium Acid Pyrophosphate (DSDP).
Described compatilizer is atactic styrene-maleic anhydride copolymer (SMA).
Described oxidation inhibitor is the Hinered phenols antioxidant 1010 or 1076 of mass ratio 1:2 and the compound of phosphite ester kind antioxidant 168.
Described lubricant is pentaerythritol stearate (PETS).
The preparation method of the PC/PBT flame-retardant alloy of above-mentioned a kind of toughening modifying, 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), add in high-speed mixer by taking dry PBT, phosphorus flame retardant, anti-molten drop agent, oxidation inhibitor and lubricant by weight ratio, after to make to stir together 3 ~ 15 minutes all mixed, discharging add in twin screw extruder carry out melt extruding, cooling granulation, obtained PBT flame-retardant master batch, and stand-by after drying;
(3), the PBT flame-retardant master batch that the PC and step (2) that take drying by weight ratio obtain is added in high-speed mixer, add the toughner, ester exchange inhibitor and the compatilizer that take by weight ratio simultaneously, after to make to stir together 3 ~ 15 minutes all mixed, discharging adds in twin screw extruder, by twin screw extruder fully plastify blended after extrude, cooling granulation, get product.
The invention has the beneficial effects as follows, compared with prior art, the present invention adopts and first prepares PBT flame-retardant master batch and for modification PC, and add appropriate toughner, ester exchange inhibitor and compatilizer, make the PC/PBT alloy system obtained not only with PC, PBT original excellent properties separately, and there is excellent flame retardant properties and shock strength, and processing fluidity is good, cost is low, and preparation technology is simple.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with concrete preferred embodiment.
Embodiment 1:
A PC/PBT flame-retardant alloy for toughening modifying, its component by mass percent proportioning is: PC 50%, PBT 26%, styrene-butadiene-methyl acrylic ester terpolymers (MBS) 8%, two (diphenyl phosphate) (RDP) 10% of Resorcinol, anti-molten drop agent 1%, triphenyl phosphite (TPPi) 1.5%, atactic styrene-maleic anhydride copolymer (SMA) 2.5%, oxidation inhibitor 0.3%, pentaerythritol stearate (PETS) 0.7%.Wherein, described PC is bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 20000 ~ 40000g/mol; Described PBT is polybutylene terephthalate; Described anti-molten drop agent is the compound of polytetrafluoroethylene (PTFE) for mass ratio 1:1 and polyvinylidene difluoride (PVDF) (PVDF); Described oxidation inhibitor is the Hinered phenols antioxidant 1010 of mass ratio 1:2 and the compound of phosphite ester kind antioxidant 168.
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), add in high-speed mixer by taking dry PBT, two (diphenyl phosphate) (RDP) of Resorcinol, anti-molten drop agent, oxidation inhibitor and pentaerythritol stearate (PETS) by weight ratio, after to make to stir together 3 ~ 15 minutes all mixed, discharging add in twin screw extruder carry out melt extruding, cooling granulation, obtained PBT flame-retardant master batch, and stand-by after drying; (3), the PBT flame-retardant master batch that the PC and step (2) that take drying by weight ratio obtain is added in high-speed mixer, add the styrene-butadiene-methyl acrylic ester terpolymers (MBS), triphenyl phosphite (TPPi) and the atactic styrene-maleic anhydride copolymer (SMA) that take by weight ratio simultaneously, after to make to stir together 3 ~ 15 minutes all mixed, discharging adds in twin screw extruder, by twin screw extruder fully plastify blended after extrude, cooling granulation, get product.
Embodiment 2:
A PC/PBT flame-retardant alloy for toughening modifying, its component by mass percent proportioning is: PC 45%, PBT 40%, Methylacrylate-Acrylate Copolymer (ACR) 4%, melamine polyphosphate (MPP) 5%, anti-molten drop agent 0.5%, Sodium Acid Pyrophosphate (DSDP) 1.5%, atactic styrene-maleic anhydride copolymer (SMA) 3%, oxidation inhibitor 0.3%, pentaerythritol stearate (PETS) 0.7%.Wherein, described PC is bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 20000 ~ 40000g/mol; Described PBT is polybutylene terephthalate; Described anti-molten drop agent is the compound of polytetrafluoroethylene (PTFE) for mass ratio 1:1 and polyvinylidene difluoride (PVDF) (PVDF); Described oxidation inhibitor is the Hinered phenols antioxidant 1076 of mass ratio 1:2 and the compound of phosphite ester kind antioxidant 168.
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), add in high-speed mixer by taking dry PBT, melamine polyphosphate (MPP), anti-molten drop agent, oxidation inhibitor and pentaerythritol stearate (PETS) by weight ratio, after to make to stir together 3 ~ 15 minutes all mixed, discharging add in twin screw extruder carry out melt extruding, cooling granulation, obtained PBT flame-retardant master batch, and stand-by after drying; (3), the PBT flame-retardant master batch that the PC and step (2) that take drying by weight ratio obtain is added in high-speed mixer, add the Methylacrylate-Acrylate Copolymer (ACR), Sodium Acid Pyrophosphate (DSDP) and the atactic styrene-maleic anhydride copolymer (SMA) that take by weight ratio simultaneously, after to make to stir together 3 ~ 15 minutes all mixed, discharging adds in twin screw extruder, by twin screw extruder fully plastify blended after extrude, cooling granulation, get product.
Claims (7)
1. the PC/PBT flame-retardant alloy of a toughening modifying, it is characterized in that, its component by mass percent proportioning is: PC 40% ~ 60%, PBT 20% ~ 40%, toughner 3% ~ 8%, phosphorus flame retardant 5% ~ 10%, anti-molten drop agent 0.1% ~ 1%, ester exchange inhibitor 0.1% ~ 1.5%, compatilizer 0.5% ~ 3%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.
2. the PC/PBT flame-retardant alloy of a kind of toughening modifying according to claim 1, is characterized in that, described toughner is styrene-butadiene-methyl acrylic ester terpolymers (MBS) or Methylacrylate-Acrylate Copolymer (ACR).
3. the PC/PBT flame-retardant alloy of a kind of toughening modifying according to claim 1, it is characterized in that, described phosphorus flame retardant is one or more in triphenylphosphate (TPP), two (diphenyl phosphate) (RDP) of Resorcinol, dihydroxyphenyl propane-bis-(diphenyl phosphate) (BDP), Resorcinol-bis-(2,6-xylyl) phosphoric acid ester (RXP), melamine polyphosphate (MPP).
4. the PC/PBT flame-retardant alloy of a kind of toughening modifying according to claim 1, is characterized in that, described anti-molten drop agent is the compound of polytetrafluoroethylene (PTFE) for mass ratio 1:1 and polyvinylidene difluoride (PVDF) (PVDF).
5. the PC/PBT flame-retardant alloy of a kind of toughening modifying according to claim 1, is characterized in that, described ester exchange inhibitor is triphenyl phosphite (TPPi) or Sodium Acid Pyrophosphate (DSDP).
6. the PC/PBT flame-retardant alloy of a kind of toughening modifying according to claim 1, is characterized in that, described compatilizer is atactic styrene-maleic anhydride copolymer (SMA).
7. the preparation method of the PC/PBT flame-retardant alloy of a kind of toughening modifying according to claim 1, is characterized in that, comprise 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), add in high-speed mixer by taking dry PBT, phosphorus flame retardant, anti-molten drop agent, oxidation inhibitor and lubricant by weight ratio, after to make to stir together 3 ~ 15 minutes all mixed, discharging add in twin screw extruder carry out melt extruding, cooling granulation, obtained PBT flame-retardant master batch, and stand-by after drying;
(3), the PBT flame-retardant master batch that the PC and step (2) that take drying by weight ratio obtain is added in high-speed mixer, add the toughner, ester exchange inhibitor and the compatilizer that take by weight ratio simultaneously, after to make to stir together 3 ~ 15 minutes all mixed, discharging adds in twin screw extruder, by twin screw extruder fully plastify blended after extrude, cooling granulation, get product.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105316791A (en) * | 2015-11-26 | 2016-02-10 | 常州市灵达化学品有限公司 | Preparing method for wear-resisting soft polyester bulked continuous filaments |
WO2018072748A1 (en) | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition and preparation method therefor |
CN108504068A (en) * | 2018-04-25 | 2018-09-07 | 横店集团得邦工程塑料有限公司 | A kind of high endurance fire retardation PC/PBT alloy material and preparation method thereof |
CN109777065A (en) * | 2017-11-15 | 2019-05-21 | 北京旭阳科技有限公司 | A kind of environmental-friendly polycarbonate/polyester composite material and preparation method and purposes |
CN109880336A (en) * | 2019-01-10 | 2019-06-14 | 金发科技股份有限公司 | A kind of polycarbonate alloy and preparation method thereof and a kind of application |
CN110423451A (en) * | 2019-08-14 | 2019-11-08 | 上海华合复合材料有限公司 | A kind of high durable based on transesterification control, the antiflaming polycarbonate alloy material of high-environmental and preparation method thereof |
CN110885545A (en) * | 2019-12-17 | 2020-03-17 | 东莞市德发塑胶科技有限公司 | Weather-resistant flame-retardant PC/PBT alloy and preparation method thereof |
US11053385B2 (en) | 2016-10-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
CN115160759A (en) * | 2022-07-26 | 2022-10-11 | 四川长虹智能制造技术有限公司 | Flame-retardant and chemical-resistant PC/PBT alloy material and preparation method and application thereof |
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2013
- 2013-12-10 CN CN201310663188.3A patent/CN104693759A/en active Pending
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105316791A (en) * | 2015-11-26 | 2016-02-10 | 常州市灵达化学品有限公司 | Preparing method for wear-resisting soft polyester bulked continuous filaments |
US10934391B2 (en) | 2016-10-21 | 2021-03-02 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
WO2018072748A1 (en) | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition and preparation method therefor |
US11053385B2 (en) | 2016-10-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
CN109777065A (en) * | 2017-11-15 | 2019-05-21 | 北京旭阳科技有限公司 | A kind of environmental-friendly polycarbonate/polyester composite material and preparation method and purposes |
CN109777065B (en) * | 2017-11-15 | 2021-07-23 | 北京旭阳科技有限公司 | Environment-friendly polycarbonate/polyester composite material and preparation method and application thereof |
CN108504068B (en) * | 2018-04-25 | 2020-06-23 | 横店集团得邦工程塑料有限公司 | High-fatigue-resistance flame-retardant PC/PBT alloy material and preparation method thereof |
CN108504068A (en) * | 2018-04-25 | 2018-09-07 | 横店集团得邦工程塑料有限公司 | A kind of high endurance fire retardation PC/PBT alloy material and preparation method thereof |
WO2020143448A1 (en) * | 2019-01-10 | 2020-07-16 | 金发科技股份有限公司 | Polycarbonate alloy, preparation method therefor and application thereof |
CN109880336A (en) * | 2019-01-10 | 2019-06-14 | 金发科技股份有限公司 | A kind of polycarbonate alloy and preparation method thereof and a kind of application |
US11767427B2 (en) | 2019-01-10 | 2023-09-26 | Kingfa Sci. & Tech. Co., Ltd. | Polycarbonate alloy and preparation method thereof and application |
CN110423451A (en) * | 2019-08-14 | 2019-11-08 | 上海华合复合材料有限公司 | A kind of high durable based on transesterification control, the antiflaming polycarbonate alloy material of high-environmental and preparation method thereof |
CN110885545A (en) * | 2019-12-17 | 2020-03-17 | 东莞市德发塑胶科技有限公司 | Weather-resistant flame-retardant PC/PBT alloy and preparation method thereof |
CN115160759A (en) * | 2022-07-26 | 2022-10-11 | 四川长虹智能制造技术有限公司 | Flame-retardant and chemical-resistant PC/PBT alloy material and preparation method and application thereof |
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Application publication date: 20150610 |