CN112480613B - Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof - Google Patents
Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a damping halogen flame-retardant reinforced PBT (polybutylene terephthalate) material, which comprises the following components in parts by weight: 30-40 parts of PBT resin, 10-15 parts of PC resin, 7-12 parts of sheet filler, 6-15 parts of damping polymer, 1-4 parts of compatilizer, 20-30 parts of glass fiber, 10-20 parts of brominated flame retardant and antimony white compound and 0.1-2 parts of processing aid. The invention discloses and reports that the polyester containing glass fiber and halogen flame retardant system in engineering plastics has damping effect for the first time; the damping halogen flame-retardant reinforced polyester material obtained by the invention has the tensile strength of more than 80MPa and the notch impact strength of 6.5kJ/m2Above (ISO standard).
Description
Technical Field
The invention relates to a damping halogen flame-retardant reinforced PBT material and a preparation method thereof, in particular to a damping halogen flame-retardant reinforced PBT material used in the fields of cooling fan frames, motor shells, sound box shells and the like in the electronic and electrical industry, belonging to the technical field of engineering plastics.
Background
Polybutylene terephthalate (PBT) has excellent electrical property, mechanical strength and processability due to crystallization and linear saturation, and the modified polyester is widely applied to the fields of electronics and electricity and the like. The flame-retardant glass fiber reinforced PBT material is commonly used as a cooling fan frame, a motor shell and other parts, and is accepted in the industry in a large quantity, but the requirements on the material are more rigorous along with the improvement of functional requirements, such as higher and higher rotating speed, smaller and smaller flame-retardant thickness and the like. The traditional material needs to be endowed with new functions, such as shock absorption and damping, and the like, so that the energy produced by the workpiece in the high-speed operation process can be effectively absorbed or alleviated, and the shock absorption is carried out to reduce the noise and improve the stability of the function of the workpiece.
A plurality of methods for realizing shock absorption and damping by using the reported polymers are disclosed, and CN01814142 and CN02830074 disclose that a thermoplastic elastomer of a multi-block copolymer obtained by a cross-linkable polymer through a dynamic cross-linking reaction has excellent shock absorption effect and is used as a sole material of footwear; CN03809473 is molded to make polypropylene into a foaming material with a buffering and damping effect; CN200980107747 discloses flame retardant composite foam prepared by mixing flame retardant, foaming agent and the like into thermoplastic elastomer, wherein the flame retardant composite foam is used for insulation, shock absorption and protection and is used in the form of plates, plane materials, pipes, sectional materials, gaskets and the like singly or compositely; CN200710100042 obtains polyurethane-vinyl polymer IPN (blending, copolymerization and interpenetrating polymer network) bi-component damping material by mixing and copolymerizing isocyanate and vinyl-containing monomer; CN201110025089 discloses that a high damping composition obtained by adding calcium carbonate or carbon black to epoxidized natural rubber and mixing calcium stearate is used for moderating or absorbing vibration energy transmission, i.e., for vibration isolation, vibration reduction, vibration isolation, etc., in order to use a high damping member containing rubber or the like as a base resin. CN201511004497 is used as an automotive interior material, and a crosslinked polymer containing a polystyrene hard segment and an ethylene branched polydiene soft segment is added into ABS resin to synergistically play a role in sound insulation and shock absorption with hollow glass beads; CN202010068682 discloses a method for preparing a polymer composite material which is prepared by direct foaming or 3D printing, and has a skin structure of polymer foam particles and at least one dynamic covalent bond on a polymer chain, and the polymer composite material is made into packaging materials, building materials, shock-absorbing materials, automobile buffer parts, sports protection products, protection parts of fitness equipment, and the like.
The above patents generally adopt polymer elastomer as matrix, or add elastomer into general plastic, and through foaming method; or a polymer containing covalent bonds is compounded to realize the damping effect, and the glass fiber-added flame-retardant damping engineering material and the realization method thereof are not reported in the publication.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the halogen flame-retardant reinforced PBT material for damping and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the damping halogen-containing flame-retardant reinforced PBT material comprises the following components in parts by weight: 30-40 parts of PBT resin, 10-15 parts of PC resin, 7-12 parts of sheet filler, 6-15 parts of damping polymer, 1-4 parts of compatilizer, 20-30 parts of glass fiber, 10-20 parts of brominated flame retardant and antimony white compound and 0.1-2 parts of processing aid.
In a halogenated flame-retardant system, the damping polymer and the flaky filler are compounded for use, the using amount of the damping polymer is not less than 6 parts, the using amount of the flaky filler is not less than 7 parts, the compounded use has a damping effect, and then 10-15 parts of PC resin is added to play a role in enhancing the damping.
According to the invention, the damping polymer is added as a second component, the flaky filler mica and the multi-block copolymerized elastomer are combined, the bromine-containing halogenated flame retardant is adopted, and the glass fiber is reinforced to obtain the PBT material with high mechanical property and damping effect.
As a preferred embodiment of the PBT material, in the brominated flame retardant and antimony white compound, the mass ratio of the brominated flame retardant to the antimony white compound is 3: 1-5.2: 1.
as a preferred embodiment of the PBT material, the PBT material comprises the following components in parts by weight: 30-40 parts of PBT resin, 10-13 parts of PC resin, 7-10 parts of sheet filler, 6-12 parts of shock-absorbing polymer, 1-2 parts of compatilizer, 20-30 parts of glass fiber, 12.5-15.5 parts of brominated flame retardant and antimony white compound and 1-1.5 parts of processing aid.
As a preferable embodiment of the PBT material, the intrinsic viscosity of the PBT resin is 0.8-1.2 dl/g; the melt flow rate of the PC resin is 3-22 g/10min, and the melt flow rate of the PC resin is measured according to ISO 1133-2011 by using 1.2kg weight and at the temperature of 300 ℃; the flaky filler is mica powder, and the mesh number of the mica powder is 40-400 meshes.
As a preferred embodiment of the PBT material, the damping polymer is a hydrogenated styrene-butadiene block copolymer, the purity of the hydrogenated styrene-butadiene block copolymer is more than 98%, the cyclohexane content in impurities is less than 0.5%, and the Shore hardness is 65-90; the compatilizer is acrylate compatilizer, and the acrylate compatilizer is at least one of ethylene-methyl acrylate binary copolymer and ethylene-acrylic ester-glycidyl methacrylate ternary copolymer.
As a preferable embodiment of the PBT material, the glass fiber is alkali-free glass fiber, the diameter of the glass fiber is 10-13 μm, and the length of the glass fiber is 3-5 mm.
As a preferred embodiment of the PBT material, the brominated flame retardant is at least one of brominated epoxy resin, brominated polystyrene, brominated polycarbonate, decabromodiphenylethane and poly (pentabromobenzyl acrylate); the processing aid is at least one of a lubricant, an ester exchange inhibitor, an antioxidant and a pigment.
As a preferable embodiment of the PBT material, the lubricant is an aliphatic carboxylic acid ester wax lubricant or a polyolefin wax lubricant, and the antioxidant is at least one of hindered phenol antioxidant, phosphite antioxidant and organic sulfur antioxidant.
In a second aspect, the invention provides a preparation method of the PBT material, which comprises the following steps:
(1) carrying out pre-drying treatment on PBT resin and PC resin, adding the dried PBT resin and PC resin, a brominated flame retardant and antimony white compound, a flaky filler, a damping polymer, a compatilizer, glass fiber and a processing aid into a high-speed stirring mixer according to a proportion, and uniformly mixing or independently feeding the mixture into a premixer through a metering feeder to obtain a mixed material;
(2) and (2) feeding the mixed material obtained in the step (1) into a double-screw extruder, fully melting and plasticizing, kneading and mixing, extruding through a machine head, bracing, cooling, granulating, drying and finally packaging under the conveying and shearing action of the double-screw extruder to obtain the damping halogen flame-retardant reinforced PBT material.
As a preferred embodiment of the preparation method, in the step (1), the pre-drying temperature is 120-140 ℃, and the pre-drying time is 4-6 hours.
In the step (2), the feeding speed of the twin-screw extruder is 450 to 800 kg/h, the temperatures of screws in the sections from the feed port to the head of the twin-screw extruder are respectively 220 to 230 ℃ in the feed section, 230 to 240 ℃ in the conveying section, 203 to 240 ℃ in the melt mixing section I, 240 to 250 ℃ in the melt mixing section II, 250 to 260 ℃ in the natural exhaust section, 240 to 250 ℃ in the mixing section I, 240 to 250 ℃ in the mixing section II, 230 to 240 ℃ in the vacuum exhaust section, 230 to 240 ℃ in the extrusion metering section, and the screw rotation speed is 250 to 400 rpm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention discloses and reports that the polyester containing glass fiber and halogen flame retardant system in engineering plastics has damping effect for the first time;
(2) the damping halogen flame-retardant reinforced polyester material obtained by the invention has the tensile strength of more than 80MPa and the notch impact strength of 6.5kJ/m2The above (ISO standard);
(3) the halogen flame-retardant reinforced polyester material for damping and damping obtained by the invention can obtain structural functional parts through molding processes such as injection molding, extrusion, mould pressing and the like, and can be widely applied to the fields of cooling fans, motor shells, sound parts, automobile buffering parts and the like in the electronic and electrical industry.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The preparation method of the PBT material in the embodiment and the comparative example comprises the following steps:
(1) drying PBT resin and PC resin at 130 deg.C for 4 hr, and controlling water content to be less than 0.03%;
(2) preparing various raw materials according to a ratio;
(3) uniformly mixing the dried PBT resin and PC resin with a brominated flame retardant and antimony white compound, a flaky filler, a damping polymer, a compatilizer, glass fiber and a processing aid in a high-speed stirring mixer in proportion or independently feeding the mixture into a premixer through a metering feeder to obtain a mixed material;
(4) feeding the mixed material into a double-screw extruder, adjusting the feeding amount to be 450-800 kg/h, wherein the temperatures of screws in all sections of the double-screw extruder from a feeding port to a machine head are respectively 230 ℃ in a feeding section, 240 ℃ in a conveying section, 240 ℃ in a melt mixing I section, 250 ℃ in a melt mixing II section, 260 ℃ in a natural exhaust section, 250 ℃ in a mixing I section, 240 ℃ in a mixing II section, 230 ℃ in a vacuum exhaust section, 230 ℃ in an extrusion metering section, and the rotating speed of the screws is 400rpm, and fully melting plasticizing, kneading and mixing, extruding, bracing, cooling, granulating, drying and finally packaging are carried out under the conveying and shearing action of the double-screw extruder to obtain the PBT material.
The test methods of the examples and comparative examples of the present invention are as follows:
(1) drying the PBT material obtained by extrusion and grain cutting at 120-130 ℃ for 3-4 hours;
(2) preparing a test sample wafer according to corresponding standard injection molding;
(3) the tensile strength is tested according to ISO 527-2012 standard, the notched Izod impact strength is tested according to ISO 180-2000 standard, the flame retardant property is tested according to UL 94-2013 standard, and the loss tangent is as follows: the damping performance was tested by a dynamic viscoelasticity tester at different temperatures with a sweep frequency.
The information on the raw materials used in the examples of the present invention and the comparative examples is as follows:
PBT resin, A1: 1200-211M of Taiwan Changchun, the intrinsic viscosity is 0.8 dl/g; a2: 1100-211M of Taiwan Changchun, the intrinsic viscosity is 1.0 dl/g; a3: characterization chemical fiber GL234, intrinsic viscosity is 1.2 dl/g;
pc resins, B1: LG chemical PC 130003 NP, melt flow rate 3g/10min (@300 ℃, 1.2 kg); b2: LG chemical PC 130010 NP, melt flow rate 10g/10min (@300 ℃, 1.2 kg); b3: LG chemical PC 130022 NP, melt flow rate 22g/10min (@300 ℃, 1.2 kg);
C. glass fiber, C1: ECS13-3.0-T436W (glass fiber diameter 13 μm, length 3.0cm, Taishan fiberglass Co., Ltd.); c2: ECS11-4.5-534A (glass fiber diameter 11 μm, length 4.5cm, boulder group);
D. mica powder, D1: AY-03N (Tahita mica materials Co., Ltd., 40 mesh); selecting D2: mica powder 400 mesh (Dachao chemical Co., Ltd.);
E. bromine flame retardant, E1: brominated epoxy F-2100, Israel ICL; e2: brominated polystyrene Saytex 621, yabao; e3: brominated polycarbonate BC-58, Kohon; e4: decabromodiphenylethane 8010, yabao; e5: polyacrylic acid pentabromobenzyl ester FR-1025, Israel ICL;
F. antimony white: selecting S-05N, Chenzhou antimony industry;
G. damping polymer: SEBS, namely S.O.E.S1605, wherein the purity of the product is more than 98%, the cyclohexane content in impurities is less than 0.5%, and the Shore hardness is 65-90;
H. a compatilizer: h1 is selected respectively: ethylene-acrylate-glycidyl methacrylate terpolymer, designation PTW (dupont); h2: ethylene-methyl acrylate dipolymer, designation ELVALOY AC 1125 (dupont);
I. processing aid: respectively selecting antioxidant (1010, 168, 412S, linaron), pigment (zinc sulfide, Hensman; black master PE2718, cabot), lubricant (PED 521, Kelaien; PETS, hair base), ester exchange inhibitor (sodium dihydrogen phosphate, Wuhan Huachuang), antioxidant accounting for 25 wt% of processing aid, pigment accounting for 10-30 wt%, lubricant accounting for 30-40 wt%, and ester exchange inhibitor accounting for 15-40 wt%.
Examples 1 to 11
The components and the use amount of the PBT material of the embodiments 1-11 are shown in Table 1, and the processing aids in the embodiments 1 and 8 are 101012.5 wt% of antioxidant, 16812.5 wt% of antioxidant, PE 271810 wt% of black masterbatch, 40 wt% of lubricant PETS and 25 wt% of sodium dihydrogen phosphate; in the embodiment 2, the processing aids comprise 101012.5 wt% of antioxidant, 16812.5 wt% of antioxidant, 30 wt% of zinc sulfide, 30 wt% of lubricant PETS and 15 wt% of sodium dihydrogen phosphate; in the embodiment 3 and the embodiment 10, the processing aids comprise 101012.5 wt% of antioxidant, 412s 12.5 wt% of antioxidant, 40 wt% of lubricant PETS and 35 wt% of sodium dihydrogen phosphate; the processing aids in the embodiments 4-6, 7, 9 and 11 comprise 101012.5 wt% of antioxidant, 16812.5 wt% of antioxidant, 35 wt% of lubricant PETS and 40 wt% of sodium dihydrogen phosphate; in comparative examples 1-4, the processing aids comprise 101012.5 wt% of antioxidant, 16812.5 wt% of antioxidant, 40 wt% of lubricant PETS, 35 wt% of sodium dihydrogen phosphate, and the performance test results of the PBT materials in examples 1-11 are shown in Table 2.
Comparative examples 1 to 4
The components and the use amount of the PBT materials of the comparative examples 1 to 4 are shown in Table 1, and the performance test results of the PBT materials of the comparative examples 1 to 4 are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from Table 2, the loss tangent of the PBT material with good damping effect is higher than that of the PBT material without damping effect, and the loss tangent is obviously increased along with the increase of frequency; the loss tangent of the PBT material without the damping effect is slightly reduced along with the increase of the frequency. The PBT material prepared by the invention has the damping effect while maintaining good mechanical property. Comparative examples 1 and 3 do not contain a PC resin, and the damping thereof is inferior to that of the present invention; comparative example 2 does not contain PC resin and damping polymer, and the damping is not as good as that of the invention; comparative example 4 does not contain a plate-like filler, and its damping is inferior to that of the present invention.
Effect example 1
In order to investigate the influence of the use amounts of the damping polymer, the flaky filler and the PC resin on the damping effect of the PBT material, test groups 1-5 and control groups 1-4 are set. In the test groups 1-5 and the control groups 1-4, only the amounts of the damping polymer, the flaky filler and the PC resin are different, as shown in Table 3; the specific selected substances of all the components are the same, and the use amounts of the other components are the same. Meanwhile, the PBT materials of the test groups 1-5 and the comparison groups 1-4 are subjected to performance tests, and the test results are shown in Table 3.
TABLE 3
As can be seen from Table 3, when the amounts of the damping polymer, the flake filler and the PC resin are within the range of the present invention, the PBT material has a good damping effect. When the PC resin is 10-13 parts, the flaky filler is 7-10 parts, and the damping polymer is 6-12 parts, the PBT material has a better damping effect.
In the control groups 4-6, the use amounts of the damping polymer, the flaky filler and the PC resin are not all in the range of the invention, and the damping effect is inferior to that of the test group 1; the control group 3 does not contain PC resin, and the damping effect is inferior to that of the test group 1; the control group 1 did not contain a vibration-damping polymer, and the control group 2 did not contain a plate-like filler, and the vibration-damping effect was far inferior to that of the test group 1. The damping polymer and the flaky filler are compounded, so that the synergistic effect is achieved, and the damping performance can be greatly improved; on the basis, the PC resin is added to play a role in enhancing the damping.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The damping halogen flame-retardant reinforced PBT material is characterized by comprising the following components in parts by weight: 30-40 parts of PBT resin, 10-15 parts of PC resin, 7-12 parts of sheet filler, 6-15 parts of damping polymer, 1-4 parts of compatilizer, 20-30 parts of glass fiber, 10-20 parts of brominated flame retardant and antimony white compound and 0.1-2 parts of processing aid; the flaky filler is mica powder, and the mesh number of the mica powder is 40-400 meshes; the damping polymer is a hydrogenated styrene-butadiene block copolymer, the purity of the hydrogenated styrene-butadiene block copolymer is more than 98%, and the Shore hardness is 65-90; in the brominated flame retardant and antimony white compound, the mass ratio of the brominated flame retardant to the antimony white compound is 3: 1-5.2: 1.
2. the PBT material of claim 1, wherein the PBT material comprises the following components in parts by weight: 30-40 parts of PBT resin, 10-13 parts of PC resin, 7-10 parts of sheet filler, 6-12 parts of shock-absorbing polymer, 1-2 parts of compatilizer, 20-30 parts of glass fiber, 12.5-15.5 parts of brominated flame retardant and antimony white compound and 1-1.5 parts of processing aid.
3. The PBT material of claim 1 or 2, wherein the PBT resin has an intrinsic viscosity of 0.8 to 1.2 dl/g; the melt flow rate of the PC resin is 3-22 g/10min, and the melt flow rate of the PC resin is measured according to ISO 1133-2011 using a 1.2kg weight and at a temperature of 300 ℃.
4. The PBT material of claim 1 or 2, wherein the compatibilizer is an acrylate compatibilizer, and the acrylate compatibilizer is at least one of an ethylene-methyl acrylate terpolymer and an ethylene-acrylate-glycidyl methacrylate terpolymer; the glass fiber is alkali-free glass fiber, the diameter of the glass fiber is 10-13 mu m, and the length of the glass fiber is 3-5 mm.
5. The PBT material of claim 1 or 2, wherein the brominated flame retardant is at least one of a brominated epoxy resin, a brominated polystyrene, a brominated polycarbonate, decabromodiphenylethane, a pentabromobenzyl polyacrylate; the processing aid is at least one of a lubricant, an ester exchange inhibitor, an antioxidant and a pigment.
6. The PBT material of claim 5, wherein the lubricant is an aliphatic carboxylic acid ester wax lubricant or a polyolefin wax lubricant, and the antioxidant is at least one of a hindered phenol antioxidant, a phosphite antioxidant, and an organic sulfur antioxidant.
7. The preparation method of the PBT material according to any one of claims 1 to 6, comprising the steps of:
(1) carrying out pre-drying treatment on PBT resin and PC resin, adding the dried PBT resin and PC resin, a brominated flame retardant and antimony white compound, a flaky filler, a damping polymer, a compatilizer, glass fiber and a processing aid into a high-speed stirring mixer according to a proportion, and uniformly mixing or independently feeding the mixture into a premixer through a metering feeder to obtain a mixed material;
(2) and (2) feeding the mixed material obtained in the step (1) into a double-screw extruder, fully melting and plasticizing, kneading and mixing, extruding through a machine head, bracing, cooling, granulating, drying and finally packaging under the conveying and shearing action of the double-screw extruder to obtain the damping halogen flame-retardant reinforced PBT material.
8. The method according to claim 7, wherein in the step (1), the pre-drying temperature is 120 to 140 ℃ and the pre-drying time is 4 to 6 hours.
9. The method according to claim 7, wherein in the step (2), the feeding speed of the twin-screw extruder is 450 to 800 kg/hr, the temperatures of screws in the sections from the feed port to the head of the twin-screw extruder are 220 to 230 ℃ in the feed section, 230 to 240 ℃ in the conveying section, 203 to 240 ℃ in the first section of melt mixing, 240 to 250 ℃ in the second section of melt mixing, 250 to 260 ℃ in the natural gas exhaust section, 240 to 250 ℃ in the first section of mixing, 240 to 250 ℃ in the second section of mixing, 230 to 240 ℃ in the vacuum gas exhaust section, 230 to 240 ℃ in the metering section of extrusion, and the screw rotation speed is 250 to 400 rpm.
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| CN202011379730.9A CN112480613B (en) | 2020-11-30 | 2020-11-30 | Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| PCT/CN2021/092854 WO2022110673A1 (en) | 2020-11-30 | 2021-05-10 | Shock-absorbing, damping, halogen-containing, flame-retardant, reinforced pbt material, and preparation method therefor |
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| CN202011379730.9A CN112480613B (en) | 2020-11-30 | 2020-11-30 | Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
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| CN112480613B (en) * | 2020-11-30 | 2021-11-30 | 金发科技股份有限公司 | Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| CN114591607B (en) * | 2022-03-17 | 2023-12-29 | 江苏金发科技新材料有限公司 | PBT composition, and preparation method and application thereof |
| CN114806129A (en) * | 2022-05-26 | 2022-07-29 | 厦门金沐实业有限公司 | PC alloy with wide damping frequency and preparation method thereof |
| CN115403899A (en) * | 2022-06-21 | 2022-11-29 | 上海大赛璐塑料工业有限公司 | Modified PBT material and preparation method thereof |
| CN114891301B (en) * | 2022-06-30 | 2024-04-26 | 广汽本田汽车有限公司 | A polypropylene composition and its preparation method and application |
| CN115709557A (en) * | 2022-10-27 | 2023-02-24 | 金旸（厦门）新材料科技有限公司 | Ultralow-melt-index high-filling halogen-free flame-retardant polypropylene material and preparation method thereof |
| CN115625816A (en) * | 2022-11-02 | 2023-01-20 | 安徽威普达材料科技有限公司 | A kind of dimensionally stable reinforced flame-retardant PET and its preparation method |
| CN115627063B (en) * | 2022-11-07 | 2024-03-22 | 金发科技股份有限公司 | Flame-retardant PBT/PC alloy material and preparation method and application thereof |
| CN115947979A (en) * | 2022-12-13 | 2023-04-11 | 安庆会通新材料有限公司 | A kind of weather-resisting composite, flame-retardant reinforced PBT composite material and preparation method thereof |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1980001167A1 (en) * | 1978-12-06 | 1980-06-12 | Gen Electric | Modified polyester compositions |
| US4467057A (en) * | 1978-12-06 | 1984-08-21 | General Electric Company | Modified polyester composition |
| JPS5716054A (en) * | 1980-07-03 | 1982-01-27 | Kuraray Co Ltd | Mica powder-filled molding resin composition |
| US6989190B2 (en) * | 2000-10-17 | 2006-01-24 | General Electric Company | Transparent polycarbonate polyester composition and process |
| KR100401326B1 (en) * | 2001-06-08 | 2003-10-10 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| JP2004091584A (en) * | 2002-08-30 | 2004-03-25 | Mitsubishi Engineering Plastics Corp | Flame retardant polybutylene terephthalate resin composition and molded article |
| US8067493B2 (en) * | 2003-12-30 | 2011-11-29 | Sabic Innovative Plastics Ip B.V. | Polymer compositions, method of manufacture, and articles formed therefrom |
| JP4884713B2 (en) * | 2005-07-04 | 2012-02-29 | ウィンテックポリマー株式会社 | Damping polybutylene terephthalate resin composition |
| CN101215409A (en) * | 2007-12-28 | 2008-07-09 | 深圳市科聚新材料有限公司 | PBT/ABS alloy material and preparation method thereof |
| CN103589128A (en) * | 2012-08-13 | 2014-02-19 | 合肥杰事杰新材料股份有限公司 | High-performance reinforced polyester alloy material and preparation method thereof |
| CN104693695B (en) * | 2013-12-05 | 2016-08-24 | 上海杰事杰新材料(集团)股份有限公司 | A kind of light noise-reducing polybutylene terephthalate (PBT) material and preparation method thereof |
| CN107130755B (en) * | 2017-05-02 | 2018-01-23 | 山东天畅环保科技股份有限公司 | A kind of glass environmental protection combined wall board |
| CN108034215B (en) * | 2017-12-28 | 2020-04-24 | 四川中物材料股份有限公司 | High-low temperature alternating-resistant modified polyester alloy material and preparation method thereof |
| CN109337302A (en) * | 2018-09-30 | 2019-02-15 | 金旸（厦门）新材料科技有限公司 | A kind of ultralow warpage high impact resistance fiberglass enhancing PBT/PC/ABS ternary-alloy material and preparation method |
| CN111286163A (en) * | 2020-02-14 | 2020-06-16 | 中广核瑞胜发（厦门）新材料有限公司 | Reinforced flame-retardant low-warpage PBT (polybutylene terephthalate) alloy material and preparation method thereof |
| CN111534021A (en) * | 2020-05-20 | 2020-08-14 | 江苏友孚汽车部件科技有限公司 | Preparation method of automobile rearview mirror shell material |
| CN112480613B (en) * | 2020-11-30 | 2021-11-30 | 金发科技股份有限公司 | Damping halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
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