CN106147156B - Halogen-free flame-retardant long fiber glass reinforced PBT composite material and preparation method - Google Patents
Halogen-free flame-retardant long fiber glass reinforced PBT composite material and preparation method Download PDFInfo
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- CN106147156B CN106147156B CN201610779342.7A CN201610779342A CN106147156B CN 106147156 B CN106147156 B CN 106147156B CN 201610779342 A CN201610779342 A CN 201610779342A CN 106147156 B CN106147156 B CN 106147156B
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/10—Copolymers of styrene with conjugated dienes
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of halogen-free flame-retardant long fiber glass reinforced PBT composite material and preparation methods.The present invention is using PBT as matrix resin, the montmorillonite of quaternary alkylphosphonium salt intercalation modifying is added as synergist, the montmorillonite of quaternary alkylphosphonium salt intercalation modifying can not only generate positive synergistic to the anti-flammability of halogen-free flame-retardant long fiber glass reinforced PBT composite material, also generate positive synergistic to the mechanical property of halogen-free flame-retardant long fiber glass reinforced PBT composite material；Compatilizer of the invention not only enhances the binding force between matrix resin and fiber, also improves the compatibility between matrix resin and toughener；Fire retardant DIDOPO melting temperature is low, and decomposition temperature is high, it is wide can to carry out processing temperature regional choice range, and the melt fluidity of DIDOPO is fabulous, it directly can carry out fire retardant and matrix resin etc. to be uniformly mixed extrusion mixing melt, continuous glass fibre is impregnated in blend melt, can be obtained finished product through cooling, traction, pelletizing.
Description
Technical field
The present invention relates to materials science field, especially a kind of halogen-free flame-retardant long fiber glass reinforced PBT composite material and its system
Preparation Method.
Background technique
PBT is crystalline thermoplastic polyester, has high-fire resistance, toughness, fatigue durability, self-lubricating, low-friction coefficient are resistance to
Hou Xing, water absorption rate are low, and only 0.1%, various physical property (including electrical property) is still kept in wet environment, electrical insulating property is heat-resisting
Water, bases, acids, oils；PBT (enhancing, modified PBT) is mainly used for automobile, electronic apparatus, industrial machinery and polymer and closes
Industry is blended in gold.Such as the distributor in automobile, body part, ignitor coil skeleton, insulating cover, exhaust system zero
Such as the deflection coil of television set, kinescope and potentiometer support, sound accompaniment output during part, motor cycle ignitor, electronic apparatus are industrial
Transformer framework, adapter skeleton switch connector, electric fan, refrigerator, motor for washer end cap, axle sleeve.Due to people couple
The requirement of product quality is higher and higher, and the performance of common short glass fiber enhancing PBT material cannot be met the requirements, long glass fiber reinforced
There is PBT the excellent performances such as high intensity, high-modulus, high thermal stability can satisfy people to high-performance pursuit；Today's society,
As the awareness of safety of people improves, and the environmental protection concept of country is constantly reinforced, and therefore, is prepared using halogen-free flame retardants fire-retardant
Material is very important project.Fire retardant is added to meeting in matrix resin since halogen-free flame retardants easily decomposes, and directly
Cause melt viscosity to increase, fire retardant and resin blend melt is made to be unable to complete the dipping to glass fibre.Currently, traditional nothing
There are two types of the fire-retardant long glass fiber reinforced composite process of halogen, and one is two-step methods (that is: to prepare fire-retardant master granule and long fibre respectively first
Dimension enhancing master batch, is then uniformly mixed and is molded), another kind is that a step cladding process (that is: prepares long glass fiber reinforced thermoplastic first
Property resin material strip, then fire retardant and matrix resin blend melt are coated in long glass fiber reinforced thermoplastic resin material strip again,
To obtain halogen-free flameproof long glass fiber reinforced thermoplastic composite).
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flame-retardant long fiber glass reinforced PBT composite material and preparation methods, it makes
Preparation Method simple process, fire retardant are uniformly dispersed, and prepare less energy consumption, and flame retardant effect is excellent, excellent combination property, and the feature of environmental protection
It is good, with overcome the deficiencies in the prior art.
The present invention is implemented as follows: halogen-free flame-retardant long fiber glass reinforced PBT composite material, in parts by weight, including
30~60 parts of polybutylene terephthalate (PBT)s, 20~40 parts of glass fibres, 9~13 parts of DIDOPO, 0.5 part of antioxidant, 3~5
Part compatilizer, 5~10 parts of toughener, 3~5 parts of triazine carbon forming agents and 1~5 portions of synergist are to prepare raw material.
The fire retardant DIDOPO is the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9 ' 10- dihydro-9-oxy of phenethyl bridge chain；
The melting temperature of DIDOPO is 180 DEG C, and decomposition temperature is 360 DEG C, and melt fluidity is excellent；DIDOPO structural formula are as follows:
The antioxidant is antioxidant 1010.
The compatilizer is SAG-008.
The toughener is POE-g-GMA or TPU.
The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
The preparation method of halogen-free flame-retardant long fiber glass reinforced PBT composite material is taken poly- to benzene two respectively by above-mentioned parts by weight
Formic acid butanediol ester, DIDOPO, triazine carbon forming agent and synergist are separately dried spare；Each component after upper above-mentioned drying and anti-
Oxygen agent, compatilizer and toughener are uniformly mixed, and carry out blending extrusion, processing temperature are as follows: and 200-235 DEG C, by impregnating runner pair
Glass fibre is impregnated, and dipping temperature is 250-270 DEG C, through cooling, traction, pelletizing, obtains the Halogen that partial size is 8~12mm
Fire-retardant long glass fiber reinforced PBT composite.
Compared with prior art, the present invention adds the montmorillonite conduct of quaternary alkylphosphonium salt intercalation modifying using PBT as matrix resin
Synergist, the montmorillonite of quaternary alkylphosphonium salt intercalation modifying can not only produce the anti-flammability of halogen-free flame-retardant long fiber glass reinforced PBT composite material
Raw positive synergistic, but also positive synergistic is generated to the mechanical property of halogen-free flame-retardant long fiber glass reinforced PBT composite material；With styrene-
The ternary atactic copolymer of acrylonitrile-methacylate ethylene oxidic ester not only enhances matrix tree as compatilizer, the compatilizer
Binding force between rouge and fiber, and also improve the compatibility between matrix resin and toughener；Fire retardant DIDOPO's
Melting temperature is low (180 DEG C), and decomposition temperature is high (360 DEG C), and it is wide to carry out processing temperature regional choice range, and
The melt fluidity of DIDOPO is fabulous, prepares halogen-free flame-retardant long fiber glass reinforced PBT composite wood using a step infusion process of the invention
Material only needs directly to carry out fire retardant and matrix resin etc. to be uniformly mixed extrusion mixing melt, and continuous glass fibre is impregnated in mixed
Melt is closed, obtains finished product, this method simple process through cooling, traction, pelletizing, fire retardant is uniformly dispersed, and flame retardant effect is excellent,
It prepares energy consumption to reduce, and product mechanical property obtained is excellent.
Specific embodiment
The embodiment of the present invention 1: halogen-free flame-retardant long fiber glass reinforced PBT composite material, in parts by weight, including 45 parts
Polybutylene terephthalate (PBT), 30 parts of glass fibres, 10 parts of DIDOPO, 0.5 part of antioxidant, 4 parts of compatilizers, 8 parts of toughener,
4 parts of triazine carbon forming agents and 1 portions of synergist are to prepare raw material；The antioxidant is antioxidant 1010；The compatilizer is
SAG-008；The toughener is POE-g-GMA；The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
The preparation method of halogen-free flame-retardant long fiber glass reinforced PBT composite material, specific solution are to take to gather to benzene two respectively
Formic acid butanediol ester, DIDOPO, triazine carbon forming agent and synergist drying for standby；By material and the antioxidant, compatible after drying
Agent and toughener are uniformly mixed, and carry out blending extrusion, processing temperature are as follows: 200-235 DEG C, by dipping runner to glass fibre into
Row dipping, dipping temperature are 260 DEG C, and cooling, traction, pelletizing obtain halogen-free flameproof long glass fiber reinforced at the particle of 8~12mm
PBT composite.
Embodiment 2: halogen-free flame-retardant long fiber glass reinforced PBT composite material, in parts by weight, including 30 parts poly- to benzene two
Formic acid butanediol ester, 40 parts of glass fibres, 13 parts of DIDOPO, 0.5 part of antioxidant, 3 parts of compatilizers, 10 parts of toughener, 5 parts of triazines
Carbon forming agent and 1 portions of synergist are to prepare raw material；The antioxidant is antioxidant 1010；The compatilizer is SAG-008；
The toughener is POE-g-GMA or TPU；The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
Preparation method is the same as implementation 1.
Embodiment 3: halogen-free flame-retardant long fiber glass reinforced PBT composite material, in parts by weight, including 60 parts poly- to benzene two
Formic acid butanediol ester, 20 parts of glass fibres, 9 parts of DIDOPO, 0.5 part of antioxidant, 5 parts of compatilizers, 5 parts of toughener, 3 parts of triazines at
Charcoal agent and 1 portions of synergist are to prepare raw material；The antioxidant is antioxidant 1010；The compatilizer is SAG-008；Institute
The toughener stated is TPU；The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
Preparation method is the same as implementation 1.
Comparative example 1: halogen-free flame-retardant long fiber glass reinforced PBT composite material, in parts by weight, including 60 parts poly- to benzene two
Formic acid butanediol ester, 20 parts of glass fibres, 9 parts of DIDOPO, 0.5 part of antioxidant, 5 parts of compatilizers, 5 parts of toughener, 3 parts of triazines at
Charcoal agent and 1 portions of synergist are to prepare raw material；The antioxidant is antioxidant 1010；The compatilizer is SAG-008；Institute
The toughener stated is TPU；The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
The preparation method (dipping cladding process) of halogen-free flameproof long fiber reinforcement PBT composite: 30 parts of PBT, 5 parts are taken respectively
Toughener and 5 parts of compatilizer drying for standby mix PBT, compatilizer and the toughener after above-mentioned drying with 0.5 part of antioxidant
It is even, then carry out blending extrusion, processing temperature is 200-235 DEG C, by the melt of extrusion by dipping runner to 20 parts of fibers into
Row dipping, obtains fiber impregnation material strip；30 parts of PBT, 5 parts of toughener, 9 parts of halogen-free flame retardants, 3 parts of triazine carbon forming agents, 5 parts are taken again
Synergist mixes the material after above-mentioned drying with 0.5 part of antioxidant, and material is added in extruder after mixing,
The mixed material of melting is coated in fiber impregnation material strip when squeezing out, pelletizing is obtained at the particle of 8~12mm after cooling
Obtain halogen-free flameproof long fiber reinforcement PBT composite.
Comparative example 2: halogen-free flame-retardant long fiber glass reinforced PBT composite material, in parts by weight, including 45 parts poly- to benzene two
Formic acid butanediol ester, 30 parts of glass fibres, 11 parts of DIDOPO, 0.5 part of antioxidant, 4 parts of compatilizers, 8 parts of toughener, 4 parts of triazines
Carbon forming agent is to prepare raw material；The antioxidant is antioxidant 1010；The compatilizer is SAG-008；The toughener
For POE-g-GMA.
Preparation method is the same as implementation 1.
Main performance test: standard testing batten is made according to standard in the product produced, and carries out every test, performance
Test result is as shown in table 1.
Table 1
According to table 1 it is known that comprehensive mechanical property is all using technical solution of the present invention preparation-obtained sample
It is higher, and flame retardant property is all V0 grades.The prepared Flame Retardancy that obtains can achieve V0 rank.The embodiment of the present invention three
Legal system is coated using the dipping that step halogen-free flame-retardant long fiber glass reinforced PBT composite material prepared by infusion process and comparative example 1 use
Standby halogen-free flame-retardant long fiber glass reinforced PBT composite material is compared, a step of embodiment three halogen-free flame-retardant long glass prepared by infusion process
Tensile strength, Izod notched impact strength, bending strength of fiber enhanced PBT composite material etc. are all than the performance in comparative example 1
Height, and the flame retardant property of the step halogen-free flame-retardant long fiber glass reinforced PBT composite material prepared by infusion process of embodiment three is V0 grades,
Comparative example 1 dipping cladding process preparation halogen-free flame-retardant long fiber glass reinforced PBT composite material flame retardant property be V1 grades, this be by
A step infusion process, which is directlyed adopt, in the present invention prepares the fire retardant of halogen-free flame-retardant long fiber glass reinforced PBT composite material in matrix melt
In be uniformly dispersed, make the excellent fireproof performance of composite material.The embodiment of the present invention one is using step Halogen resistance prepared by infusion process
It fires long glass fiber reinforced PBT composite and comparative example 2 is all using step halogen-free flame-retardant long fiber glass reinforced PBT prepared by infusion process
Composite material is compared, and that synergist is not added in comparative example 2, the halogen-free flame-retardant long fiber glass reinforced PBT composite material of comparative example 2 is drawn
Intensity, bending, impact property and anti-flammability performance are stretched all without the good of embodiment one, this shows that synergistic is added in embodiment one
Agent not only generates positive synergistic to the mechanical property of halogen-free flame-retardant long fiber glass reinforced PBT composite material, and to halogen-free flame-retardant long glass
The flame retardant property of fiber enhanced PBT composite material generates positive synergistic.
Claims (6)
1. a kind of halogen-free flame-retardant long fiber glass reinforced PBT composite material, it is characterised in that: in parts by weight, including 30~60
Part polybutylene terephthalate (PBT), 20~40 parts of glass fibres, 9~13 parts of fire retardant DIDOPO, 0.5 part of antioxidant, 3~5
Part compatilizer, 5~10 parts of toughener, 3~5 parts of triazine carbon forming agents and 1~5 portions of synergist are to prepare raw material；Poly- pair is taken respectively
Benzene dicarboxylic acid butanediol ester, DIDOPO, triazine carbon forming agent and synergist are separately dried spare；Each component after above-mentioned drying with
Antioxidant, compatilizer and toughener are uniformly mixed, and carry out blending extrusion, processing temperature are as follows: and 200-235 DEG C, by impregnating runner
Glass fibre is impregnated, dipping temperature is 250-270 DEG C, through cooling, traction, pelletizing, obtains the nothing that partial size is 8~12mm
The fire-retardant long glass fiber reinforced PBT composite of halogen；The synergist is the montmorillonite of quaternary alkylphosphonium salt intercalation modifying.
2. halogen-free flame-retardant long fiber glass reinforced PBT composite material according to claim 1, it is characterised in that: described is fire-retardant
Agent DIDOPO is phenethyl bridge chain 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide；The melting temperature of DIDOPO is
180 DEG C, decomposition temperature is 360 DEG C, and melt fluidity is excellent；DIDOPO structural formula are as follows:
3. halogen-free flame-retardant long fiber glass reinforced PBT composite material according to claim 1, it is characterised in that: the antioxygen
Agent is antioxidant 1010.
4. halogen-free flame-retardant long fiber glass reinforced PBT composite material according to claim 1, it is characterised in that: described is compatible
Agent is SAG-008.
5. halogen-free flame-retardant long fiber glass reinforced PBT composite material according to claim 1, it is characterised in that: the toughening
Agent is POE-g-GMA or TPU.
6. a kind of preparation method of halogen-free flame-retardant long fiber glass reinforced PBT composite material as described in claim 1, feature exist
In: above-mentioned parts by weight are pressed, take polybutylene terephthalate (PBT), DIDOPO, triazine carbon forming agent and synergist difference respectively
Drying for standby；Each component after above-mentioned drying is uniformly mixed with antioxidant, compatilizer and toughener, carries out blending extrusion, processing
Temperature are as follows: 200-235 DEG C, glass fibre is impregnated by impregnating runner, dipping temperature is 250-270 DEG C, through cooling, is led
Draw, pelletizing, obtains the halogen-free flame-retardant long fiber glass reinforced PBT composite material that partial size is 8~12mm.
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| CN106751576A (en) * | 2016-12-26 | 2017-05-31 | 安徽元通采暖科技有限公司 | The special refractory seals packing ring of fireplace smoke discharging pipe |
| JP7114895B2 (en) | 2017-12-19 | 2022-08-09 | 三菱ケミカル株式会社 | polyethylene terephthalate film |
| CN108485208A (en) * | 2018-03-29 | 2018-09-04 | 贵州省材料产业技术研究院 | A kind of DOPO derivatives Flame-retardant PET transparent composite and preparation method |
| CN108929524A (en) * | 2018-09-05 | 2018-12-04 | 贵州省材料产业技术研究院 | A kind of increasing reaction flame-retardant polyester material and preparation method thereof |
| CN110923841B (en) * | 2019-11-13 | 2022-05-31 | 上海力道新材料科技股份有限公司 | Flame-retardant polyester fiber and preparation method thereof |
| CN112980162B (en) * | 2021-03-19 | 2022-04-15 | 西南科技大学 | Montmorillonite modified PET high-temperature-resistant optical polyester material and preparation method thereof |
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| CN102875982A (en) * | 2012-10-15 | 2013-01-16 | 宁波优科泰科技发展有限公司 | In-situ modified halogen-free flame retardant thermoplastic resin composition and preparation method thereof |
| CN104086593A (en) * | 2014-07-14 | 2014-10-08 | 中国科学院宁波材料技术与工程研究所 | DOPO derivatives as well as preparation method and application thereof |
| CN104371291A (en) * | 2014-12-01 | 2015-02-25 | 贵州凯科特材料有限公司 | High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof |
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| CN102875982A (en) * | 2012-10-15 | 2013-01-16 | 宁波优科泰科技发展有限公司 | In-situ modified halogen-free flame retardant thermoplastic resin composition and preparation method thereof |
| CN104086593A (en) * | 2014-07-14 | 2014-10-08 | 中国科学院宁波材料技术与工程研究所 | DOPO derivatives as well as preparation method and application thereof |
| CN104371291A (en) * | 2014-12-01 | 2015-02-25 | 贵州凯科特材料有限公司 | High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof |
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