CN104610713A - High-dielectric and high-heat-resistance PBT glass fiber reinforced material for automobile ignition coils and preparation method of high-dielectric and high-heat-resistance PBT glass fiber reinforced material - Google Patents
High-dielectric and high-heat-resistance PBT glass fiber reinforced material for automobile ignition coils and preparation method of high-dielectric and high-heat-resistance PBT glass fiber reinforced material Download PDFInfo
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- CN104610713A CN104610713A CN201510056899.3A CN201510056899A CN104610713A CN 104610713 A CN104610713 A CN 104610713A CN 201510056899 A CN201510056899 A CN 201510056899A CN 104610713 A CN104610713 A CN 104610713A
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Abstract
The invention relates to a high-dielectric and high-heat resistance PBT glass fiber reinforced material for automobile ignition coils and a preparation method of the high-dielectric and high-heat resistance PBT glass fiber reinforced material. The glass fiber reinforced material comprises the following raw material components in parts by weight: 35-69 parts of butanediol polyterephthalate, 10-30 parts of 1,4-cyclohexanedimethanol polyterephthalate, 20-30 parts of short glass fiber; 1-5 parts of nanometer metal particles, 0.1-0.5 part of carbon nano tube, 0.1-0.5 part of a coupling reagent, 0.5-1.5 parts of a nucleating agent, 1-2 parts of a crystallization promoting agent, 0.1-0.5 part of a lubricant and 0.1-0.5 part of an antioxygen. Compared with the prior art, the PBT glass fiber reinforced material is good in heat resistance, excellent in dielectric property and high in physical property retention.
Description
Technical field
The present invention relates to PBT glass fiber reinforced materials, be specifically related to the high heat-resisting PBT glass fiber reinforced materials of the high dielectric of a kind of automobile ignition coil.
Background technology
Along with automotive gasoline engine is to the future development of high rotating speed, high compression ratio, high-power, low oil consumption and low emission, traditional portfire is not suitable with service requirements.The core component of portfire is spark coil and switching arrangement, improves the energy of spark coil, and sparking plug just can produce the spark of enough energy, and this is the primary condition that portfire adapts to Modern Engine operation.In fact spark coil is exactly a transformer (there are armature winding, secondary winding, iron core, megohmite etc. in the inside), by the voltage that the voltage transition of 12 volts, automobile is 2-3 ten thousand volts, automotive ignition system utilizes this high voltage electric to give me a little gas mixture in gas cylinder.Spark coil all plays critical effect for the performance and safety performance etc. of automobile, and the material therefore for automobile ignition coil often requires higher thermotolerance and dielectric strength.
Polybutylene terephthalate (PBT) is the very fast engineering thermoplastic's material of a kind of crystallization rate, be easy to realize high-speed molding, its electrical property is excellent, arc resistance is good, solvent resistance is extremely excellent, but its product molding shrinking percentage is larger, there is the shortcomings such as rigidity under notched Izod impact strength low and high temperature is not enough, glass fibre reinforced modifiedly effectively can improve the above-mentioned defect of PBT material, but common PBT glass fiber reinforced materials is heat-resisting still relative on the low side with dielectric properties, be difficult to the high standard requirement meeting automobile ignition wire loop material, limit the application in its this field.
Poly terephthalic acid 1,4-cyclohexanedimethanoester ester (PCT) is a kind of thermoplastic polyester of high temperature resistant, semicrystalline, its character is similar with polybutylene terephthalate (PBT) to polyethylene terephthalate (PET), there is the intensity of PBT, toughness, and thermotolerance is better than PET; PCT has higher thermotolerance, although its resistance toheat is lower than polyphenylene sulfide (PPS), high-temperature liquid crystalline polymer (LCPS) and heat resistant polyamide, higher than middle temperature liquid crystalline polymers and other polyester; Simultaneously because PCT and PBT is all polyester, the two has good consistency, makes with PBT is blended the resistance toheat that alloy can significantly improve PBT material.
PBT glass fiber reinforced materials has excellent manufacturability and mechanical property, but its dielectric strength is lower, is difficult to meet the requirement of automobile ignition coil to high dielectric strength material.Generally speaking, material is made to obtain high dielectric property often through a large amount of ceramic-like of interpolation or conductor class filler, and adding of a large amount of fillers often makes the mechanical property of material significantly lose, thus how under the prerequisite ensureing material high dielectric property, improve material mechanical performance conservation rate, the PBT glass fiber reinforced materials obtaining excellent mechanical properties is most important.
Summary of the invention
Object of the present invention is exactly provide the high dielectric of a kind of automobile ignition coil high heat-resisting PBT glass fiber reinforced materials to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A kind of automobile ignition coil high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, the raw material of this glass fiber reinforced materials comprises the component of following parts by weight proportioning:
The limiting viscosity of described polybutylene terephthalate is 0.8 ~ 1.2Dl/g; Described poly terephthalic acid 1,4 cyclohexane dimethanol ester is relative density 1.19g/cm
3, melt temperature is the semicrystalline poly terephthalic acid 1,4 cyclohexane dimethanol ester of 280 ~ 290 DEG C.
Described short glass fiber is the alkali-free short glass fiber of diameter 9 ~ 14 μm, chopped length 2 ~ 5mm; Described nano-metal particle is the mixture of one or more in Ag, Al, Ni nano particle; Described carbon nanotube is the multi-walled carbon nano-tubes of diameter 2 ~ 5nm; Described coupling agent is the compound of one or more in silane coupling agent, organic titanate, organo-metallic sequestrant, phosphoric acid ester; Described nucleator is the mixture of one or more in nano imvite, attapulgite, mica powder; Described crystallization promoter is the compound of one or more in PEG-400-2-Ethyl Hexanol, PEG-4-dilaurate, neo-pentyl ethylene glycol Biphenyl Ester, triglycol Biphenyl Ester.
Described lubricant is the compound of one or more in low molecular weight polyethylene, stearic amide, methylene bis stearic amide, N, N-ethylene bis stearic acid amide, pentaerythritol stearate; Described oxidation inhibitor is selected from the compound of one or more in irgasfos 168, antioxidant 1010, antioxidant 1076, oxidation inhibitor 245.
An automobile ignition coil preparation method for the high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, this preparation method comprises the following steps:
(1) get the raw materials ready according to following parts by weight of component: polybutylene terephthalate 35 ~ 69 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester 10 ~ 30 parts, short glass fiber 20 ~ 30 parts, nano-metal particle 1 ~ 5 part, carbon nanotube 0.1 ~ 0.5 part, coupling agent 0.1 ~ 0.5 part, nucleator 0.5 ~ 1.5 part, crystallization promoter 1 ~ 2 part, lubricant 0.1 ~ 0.5 part, 0.1 ~ 0.5 part, oxidation inhibitor;
(2) each raw material described in step (1) is put into high mixer to mix, obtain Preblend;
(3) Preblend that step (2) obtains is added twin screw extruder, controlling twin screw extruder each section of extruder temperature is 240 ~ 270 DEG C, and screw speed, at 300 ~ 500 revs/min, melt extrudes granulation.
Polyester PCT and the PBT that the present invention adopts resistance toheat splendid is blended makes alloy, and coordinates nucleator and crystallization promoter to improve crystallization, significantly improves the thermotolerance of PBT strongthener; Adopt efficient inorganic nucleation to improve material crystalline, it is different from organic nucleating agent can not make material produce degraded simultaneously, thus is ensureing that the same season of material crystalline and heat-resisting effect, it had higher mechanical property conservation rate; Generally speaking, material is made to obtain high dielectric property often through a large amount of ceramic-like of interpolation or conductor class filler, and adding of a large amount of fillers often makes the mechanical property of material significantly lose, one aspect of the present invention helps Nano filling to disperse better by adding suitable coupling agent, add on the one hand carbon nanotube and Nano filling to produce synergistic effect and improve dielectric effect, thus significantly reduce the consumption of Nano filling, reduce PBT strongthener mechanical property loss of energy.
Compared with prior art, PBT glass fiber reinforced materials Good Heat-resistance prepared by the present invention, heat-drawn wire (HDT) can reach more than 225 DEG C, there are excellent dielectric properties simultaneously, dielectric strength can reach more than 30kV/mm, material mechanical performance conservation rate is high in addition, and physical and mechanical properties is excellent, can meet the service requirements of automobile ignition wire loop material.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
In following examples and comparative example, the limiting viscosity of polybutylene terephthalate PBT used is 0.8 ~ 1.2Dl/g; The semicrystalline poly terephthalic acid 1,4 cyclohexane dimethanol ester that poly terephthalic acid 1,4 cyclohexane dimethanol ester used is relative density is 1.19g/cm3, melt temperature is 280 ~ 290 DEG C.
Embodiment 1
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 35 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 30 parts, short glass fiber 30 parts, nano-metal particle 5 parts, carbon nanotube 0.5 part, coupling agent 0.5 part, nucleator 1.5 parts, crystallization promoter 2 parts, lubricant 0.3 part, 0.3 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 2
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 35 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 30 parts, short glass fiber 30 parts, nano-metal particle 5 parts, carbon nanotube 0.5 part, coupling agent 0.5 part, nucleator 0.5 part, crystallization promoter 1 part, lubricant 0.3 part, 0.3 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 3
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 40 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 30 parts, short glass fiber 25 parts, nano-metal particle 5 parts, carbon nanotube 0.1 part, coupling agent 0.5 part, nucleator 1 part, crystallization promoter 1.5 parts, lubricant 0.1 part, 0.1 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 4
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 52 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 20 parts, short glass fiber 25 parts, nano-metal particle 3 parts, carbon nanotube 0.3 part, coupling agent 0.3 part, nucleator 1.5 parts, crystallization promoter 2 parts, lubricant 0.5 part, 0.5 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 5
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 69 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 10 parts, short glass fiber 20 parts, nano-metal particle 1 part, carbon nanotube 0.5 part, coupling agent 0.1 part, nucleator 1.5 parts, crystallization promoter 2 parts, lubricant 0.3 part, 0.3 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 6
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 35 parts, poly terephthalic acid 1,4 cyclohexane dimethanol ester PCT 30 parts, short glass fiber 30 parts, nanometer Ag metallic particles 5 parts, carbon nanotube 0.5 part, silane coupling agent 0.5 part, nano imvite 1.5 parts, PEG-400-2-Ethyl Hexanol 2 parts, low molecular weight polyethylene 0.1 part, irgasfos 168 0.1 part, antioxidant 1010 0.4 part.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 7
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 45 parts, poly terephthalic acid 1,4 cyclohexane dimethanol ester PCT 20 parts, short glass fiber 25 parts, nanometer Al metallic particles 4 parts, carbon nanotube 0.1 part, organo-metallic sequestrant 0.2 part, phosphoesterase 30 .1 part, nano imvite 0.5 part, attapulgite 0.5 part, PEG-4-dilaurate 2 parts, stearic amide 0.2 part, methylene bis stearic amide 0.3 part, antioxidant 1076 0.1 part.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 400 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Embodiment 8
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 45 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 20 parts, short glass fiber 25 parts, the mixed metal particles of nanometer Al and Ni nanoparticle 2 parts, carbon nanotube 0.1 part, organic titanate 0.1 part, mica powder 1.5 parts, neo-pentyl ethylene glycol Biphenyl Ester 1 part, triglycol Biphenyl Ester 1 part, 0.2 part of N, the compound that N-ethylene bis stearic acid amide and 0.1 part of pentaerythritol stearate form, 0.2 part of irgasfos 168,0.3 part of oxidation inhibitor 245.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 400 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Comparative example 1
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 70 parts, short glass fiber 30 parts, lubricant 0.3 part, 0.3 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 240 ~ 260 DEG C, and screw speed is 300 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Comparative example 2
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 35 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester PCT 30 parts, short glass fiber 30 parts, nano-metal particle 5 parts, carbon nanotube 0.5 part, coupling agent 0.5 part, organic nucleating agent SURLYN 89201.5 parts, crystallization promoter 2 parts, lubricant 0.3 part, 0.3 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
Comparative example 3
Get the raw materials ready according to following parts by weight component: polybutylene terephthalate PBT 25 parts, poly terephthalic acid 1,4 cyclohexane dimethanol ester PCT 30 parts, short glass fiber 30 parts, nano-metal particle 15 parts, nucleator 1.5 parts, crystallization promoter 2 parts, lubricant 0.3 part, 0.3 part, oxidation inhibitor.
Above-mentioned each raw material is put into high mixer mix, obtain Preblend.Then add in twin screw extruder by Preblend, through melt extruding granulation, twin screw extruder each section of extruder temperature controls between 250 ~ 270 DEG C, and screw speed is 500 revs/min.The particle obtained was 100 DEG C of dryings 2 hours, and get product material.
The material that PBT glass fiber reinforced materials embodiment 1 ~ embodiment 8 prepared and comparative example 1 ~ comparative example 3 obtain is injection molded into the standard batten tested by standard size, carry out performance test.Each performance test standard is as shown in table 1, and each the performance test results is as shown in table 2.
The each performance test standard of table 1
| Physicals | Testing method |
| Tensile strength | ISO 527-2 |
| Flexural strength | ISO 178 |
| Modulus in flexure | ISO 178 |
| Intact shock strength | ISO 179 |
| Notched Izod impact strength | ISO 179 |
| Heat-drawn wire 1.82MPa | ISO 75-2/A |
| Dielectric strength | IEC 243 |
The each the performance test results of table 2
Claims (10)
1. the automobile ignition coil high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, the raw material of this glass fiber reinforced materials comprises the component of following weight:
2. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, the limiting viscosity of described polybutylene terephthalate is 0.8 ~ 1.2Dl/g; Described poly terephthalic acid 1,4 cyclohexane dimethanol ester is relative density 1.19g/cm
3, melt temperature is the semicrystalline poly terephthalic acid 1,4 cyclohexane dimethanol ester of 280 ~ 290 DEG C.
3. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described short glass fiber is the alkali-free short glass fiber of diameter 9 ~ 14 μm, chopped length 2 ~ 5mm.
4. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described nano-metal particle is the mixture of one or more in Ag, Al, Ni nano particle.
5. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described carbon nanotube is the multi-walled carbon nano-tubes of diameter 2 ~ 5nm.
6. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described coupling agent is the compound of one or more in silane coupling agent, organic titanate, organo-metallic sequestrant, phosphoric acid ester.
7. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described nucleator is the mixture of one or more in nano imvite, attapulgite, mica powder.
8. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described crystallization promoter is the compound of one or more in PEG-400-2-Ethyl Hexanol, PEG-4-dilaurate, neo-pentyl ethylene glycol Biphenyl Ester, triglycol Biphenyl Ester.
9. the automobile ignition coil according to claim 1 high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, described lubricant is the compound of one or more in low molecular weight polyethylene, stearic amide, methylene bis stearic amide, N, N-ethylene bis stearic acid amide, pentaerythritol stearate; Described oxidation inhibitor is selected from the compound of one or more in irgasfos 168, antioxidant 1010, antioxidant 1076, oxidation inhibitor 245.
10. an automobile ignition coil as claimed in claim 1 preparation method for the high heat-resisting PBT glass fiber reinforced materials of high dielectric, it is characterized in that, this preparation method comprises the following steps:
(1) get the raw materials ready according to following parts by weight of component: polybutylene terephthalate 35 ~ 69 parts, poly terephthalic acid 1,4-cyclohexanedimethanoester ester 10 ~ 30 parts, short glass fiber 20 ~ 30 parts, nano-metal particle 1 ~ 5 part, carbon nanotube 0.1 ~ 0.5 part, coupling agent 0.1 ~ 0.5 part, nucleator 0.5 ~ 1.5 part, crystallization promoter 1 ~ 2 part, lubricant 0.1 ~ 0.5 part, 0.1 ~ 0.5 part, oxidation inhibitor;
(2) each raw material described in step (1) is put into high mixer to mix, obtain Preblend;
(3) Preblend that step (2) obtains is added twin screw extruder, controlling twin screw extruder each section of extruder temperature is 240 ~ 270 DEG C, and screw speed, at 300 ~ 500 revs/min, melt extrudes granulation.
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Cited By (8)
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| CN105440601A (en) * | 2015-12-21 | 2016-03-30 | 东莞市美塑塑料科技有限公司 | PBT/PCT synthesis material |
| CN106117987A (en) * | 2016-07-04 | 2016-11-16 | 安徽祈艾特电子科技股份有限公司 | A kind of high dielectric PBT material with epoxy bond and preparation method thereof |
| CN108084675A (en) * | 2018-02-06 | 2018-05-29 | 杨秀枝 | A kind of preparation method and applications for the dielectric composite material for adding zirconium dioxide |
| CN109679304A (en) * | 2018-12-28 | 2019-04-26 | 深圳市中塑新材料有限公司 | A kind of PBT/PCT composite material and preparation method and purposes |
| CN113354927A (en) * | 2021-06-23 | 2021-09-07 | 广东虹勤通讯技术有限公司 | Fiber reinforced polyester-based polymer material |
| CN114685953A (en) * | 2020-04-30 | 2022-07-01 | 华润化学材料科技股份有限公司 | Modified polyester material, composite sandwich board prepared from modified polyester material and preparation method of composite sandwich board |
| CN114685952A (en) * | 2022-02-28 | 2022-07-01 | 金发科技股份有限公司 | PBT composite material and preparation and application thereof |
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| CN102964785A (en) * | 2012-12-04 | 2013-03-13 | 上海日之升新技术发展有限公司 | Halogen-free flame retardant reinforced PCT/polyester alloy and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105440601A (en) * | 2015-12-21 | 2016-03-30 | 东莞市美塑塑料科技有限公司 | PBT/PCT synthesis material |
| CN106117987A (en) * | 2016-07-04 | 2016-11-16 | 安徽祈艾特电子科技股份有限公司 | A kind of high dielectric PBT material with epoxy bond and preparation method thereof |
| CN108084675A (en) * | 2018-02-06 | 2018-05-29 | 杨秀枝 | A kind of preparation method and applications for the dielectric composite material for adding zirconium dioxide |
| CN109679304A (en) * | 2018-12-28 | 2019-04-26 | 深圳市中塑新材料有限公司 | A kind of PBT/PCT composite material and preparation method and purposes |
| CN114685953A (en) * | 2020-04-30 | 2022-07-01 | 华润化学材料科技股份有限公司 | Modified polyester material, composite sandwich board prepared from modified polyester material and preparation method of composite sandwich board |
| CN113354927A (en) * | 2021-06-23 | 2021-09-07 | 广东虹勤通讯技术有限公司 | Fiber reinforced polyester-based polymer material |
| CN114685952A (en) * | 2022-02-28 | 2022-07-01 | 金发科技股份有限公司 | PBT composite material and preparation and application thereof |
| CN115011081A (en) * | 2022-06-10 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Glass fiber reinforced PET composition with rapid crystallization and preparation method thereof |
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Application publication date: 20150513 |