CN104403283A - Ceramic fiber reinforced flame retardant PBT (polybutylene terephthalate) material and preparation method thereof - Google Patents
Ceramic fiber reinforced flame retardant PBT (polybutylene terephthalate) material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ceramic fiber reinforced flame retardant PBT (polybutylene terephthalate) material and a preparation method thereof. PBT, ceramic fiber, a coupling agent, a flame retardant, a floating fiber elimination agent, an antioxidant, a toughening agent and a dispersant are taken as raw materials. The preparation method comprises steps as follows: the raw materials are mixed in a high-speed mixer, the mixture is added to a double-screw extruder, in the extruding process, the ceramic fiber is metered by a lateral precise feeding system and uniformly added, the mixture is subjected to extruding, pulling, cooling, granulating and drying, and a final product is obtained. On the basis that little ceramic fiber is added, the mechanical property and the flame retardant property of the materials can be improved, and influence of fiber on the appearance of the PBT material is reduced; and with adding of the dispersing agent, the balling rate of the ceramic fiber is reduced, uniform dispersity of the ceramic fiber is improved, and the PBT resin reinforcement effect is further enhanced.
Description
Technical field
The invention relates to resin-reinforcing technique field, is specifically related to ceramic fiber and strengthens flame-retardant PBT material and preparation method thereof.
Background technology
Ceramic fiber is a kind of collection fibrous light refractory materials, its diameter is generally 2 μm ~ 5 μm, length mostly is 30mm ~ 250mm, ceramic fiber has excellent heat-proof quality and less volume density, be used for industry insulation, sealing, the insulation of protective material, electric heating device, lagging material, the insulation of plant and instrument, electrical heating element and heat insulation material, automobile industry lagging material etc.
Polybutylene terephthalate (being called for short PBT) arrives opaque, crystalline thermoplastic polyester for oyster white is translucent, PBT has high physical strength, high heat resistance and electrical insulating property, and the feature of the mechanical property of its excellence, electric property and easily processing makes it be widely used in electronic apparatus and auto industry field.But PBT shortcoming is that notched Izod impact strength is low, and molding shrinkage is large.Therefore prior art adopts glass fiber reinforcement or inorganic fill modification usually, can make its tensile strength, flexural strength is enhanced about more than once, heat-drawn wire also significantly improves.But to strengthen material, often need to add relatively large glass fibre, the membership that adds of a large amount of glass fibre affects material and appearance property, in addition, flame retardant resistance and the resistivity against fire of glass fibre are poor, can not meet the temperature requirement of PBT material when the product such as electronic component and electricity-saving lamp uses.
In background technology, yet there are no and introduce the pertinent literature of ceramic fiber as PBT material enhancement component, compared with glass fibre, ceramic fiber can tolerate higher temperature, and mechanical property is more excellent, only needs less addition to meet reinforced effects.
Using ceramic fiber as the enhancement component of resin, problems of the prior art are: because ceramic fiber length-to-diameter ratio is large, surface charge is uneven, consequent machinery tangles power, electrostatic force etc. and makes ceramic fiber in dispersion medium, be difficult to dispersion, the clustering phenomena of easy generation fiber, fiber is glomeration gradually, just becomes ceramic fiber ball, and the existence of ceramic fiber ball can make reinforced effects greatly reduce.
Summary of the invention
The problem that the invention will solve is on the basis of adding a small amount of ceramic fiber, improves mechanical property and the flame retardant properties of material, reduces the impact of fiber on PBT material outward appearance; By adding dispersion agent, reducing ceramic fiber balling ratio, improving the uniformly dispersed of ceramic fiber, further enhancing the reinforced effects to PBT resin.
For solving the problems of the technologies described above, the technical scheme that the invention adopts is: a kind of ceramic fiber strengthens flame-retardant PBT material, is made up of following component by weight percentage:
Preferably, the density of described PBT resin is 1.31 ~ 1.40g/cm3, fusing point 220 ~ 240 DEG C, and test condition is 230 DEG C, and standard test load is 2.16Kg.
Preferably, described ceramic fiber is the ceramic fiber of high temperature (HT) type, Fibre diameter 2 ~ 4 microns.
Preferably, described coupling agent component is: one or more in phosphate coupling agent, silane coupling agent, glycidyl ester.
Preferably, described fire retardant is one or more in organic hypophosphite, melamine polyphosphate, melamine cyanurate, antimonous oxide, sodium pyroantimoniate, zinc borate.
Preferably, described floating fine remover is TAF.
Preferably, described oxidation inhibitor is β (3,5-di-tert-butyl-hydroxy phenyl) propionate, two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, one or more in thio-2 acid 2 stearyl ester.
Preferably, described toughner is one in ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW) or its mixture.
Preferably, described dispersion agent is Vltra tears (HPMC), the one in polyacrylamide (PAM) or its mixture.
The invention additionally provides the preparation method that a kind of ceramic fiber strengthens flame-retardant PBT material, and concrete steps are as follows:
1) PBT, coupling agent, fire retardant, floating fine remover, oxidation inhibitor, toughner and dispersion agent are mixed 3.5min in high-speed mixer;
2) above-mentioned miscellany is added length-to-diameter ratio is 32: 1 ~ 40: 1, rotating speed is in the twin screw extruder of 350-450rpm, its expressing technique each district temperature range is 200 ~ 240 DEG C, residence time 1-2 minute, and pressure is 12-18Mpa;
3) in extrusion, ceramic fiber is evenly added by the accurate feed system metering of side direction, obtains the finished product after extruding tie rod, cooling, pelletizing, drying.
The advantage that the invention has and positively effect are:
1. use ceramic fiber to replace conventional fiber glass as the enhancement component of PBT material, because Mechanical Property of Ceramics is more excellent, only need less addition can meet enhancing requirement, reduce the impact of interpolation on product appearance of fiber.
2. adding of ceramic fiber the resistivity against fire of PBT material and flame retardant resistance are improved further.
3. with the addition of dispersion agent, reduce ceramic fiber balling ratio, improve the uniformly dispersed of ceramic fiber, further enhance the reinforced effects to PBT material.
Embodiment
Below in conjunction with specific embodiment, the invention is described further.
Embodiment 1
1. by 77.2 kilograms of PBT resin, 0.1 kg of phosphoric acid ester coupling agent, 0.1 kilogram of silane coupling agent, 3 kilograms of organic hypophosphite, 3 kilograms of melamine polyphosphates, 2 kilograms of antimonous oxides, 2 kilograms of zinc borates, 0.2 kilogram of TAF, 0.1 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 0.1 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 1 kilogram of ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), 1 kilogram of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), 0.2 kilogram of Vltra tears (HPMC) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 10 kilograms of ceramic fibers are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 95 |
| Notched Izod impact strength | J/M | ISO 180 | 86 |
| Flexural strength | MPa | ISO 178 | 157 |
| Modulus in flexure | MPa | ISO 178 | 6500 |
| Heat-drawn wire (1.82Mpa) | ℃ | ISO 75-1 | 194 |
| Density | g/cm 3 | ISO 1183 | 1.45 |
| Flame retardant properties | -- | UL-94 | 1.6V-0 |
Embodiment 2
1. by 67.2 kilograms of PBT resin, 0.2 kg of phosphoric acid ester coupling agent, 0.3 kilogram of glycidyl ester, 4 kilograms of organic hypophosphite, 4 kilograms of melamine polyphosphates, 3 kilograms of antimonous oxides, 2 kilograms of zinc borates, 0.4 kilogram of TAF, 0.2 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 0.3 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 1 kilogram of ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), 2 kilograms of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymers (PTW), 0.4 kilogram of Vltra tears (HPMC) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 15 kilograms of ceramic fibers are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 114 |
| Notched Izod impact strength | J/M | ISO 180 | 99 |
| Flexural strength | MPa | ISO 178 | 181 |
| Modulus in flexure | MPa | ISO 178 | 7900 |
| Heat-drawn wire (1.82Mpa) | ℃ | ISO 75-1 | 197 |
| Density | g/cm 3 | ISO 1183 | 1.52 |
| Flame retardant properties | -- | UL-94 | 1.6V-0 |
Embodiment 3
1. by 55.9 kilograms of PBT resin, 0.5 kg of phosphoric acid ester coupling agent, 0.5 kilogram of silane coupling agent, 5 kilograms of organic hypophosphite, 5 kilograms of melamine polyphosphates, 6 kilograms of zinc borates, 0.5 kilogram of TAF, 0.5 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 0.5 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 2 kilograms of ethylene-methyl acrylate-glyceryl methacrylate multipolymers (EMAG), 3 kilograms of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymers (PTW), 0.6 kilogram of Vltra tears (HPMC) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 20 kilograms of ceramic fibers are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 126 |
| Notched Izod impact strength | J/M | ISO 180 | 118 |
| Flexural strength | MPa | ISO 178 | 204 |
| Modulus in flexure | MPa | ISO 178 | 9400 |
| Heat-drawn wire (1.82Mpa) | ℃ | ISO 75-1 | 199 |
| Density | g/cm 3 | ISO 1183 | 1.55 |
| Flame retardant properties | -- | UL-94 | 1.6V-0 |
Embodiment 4
1. by 45.4 kilograms of PBT resin, 0.7 kilogram of silane coupling agent, 0.8 kilogram of glycidyl ester, 6 kilograms of organic hypophosphite, 6 kilograms of melamine polyphosphates, 6 kilograms of antimonous oxides, 0.8 kilogram of TAF, 0.7 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 0.8 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 3 kilograms of ethylene-methyl acrylate-glyceryl methacrylate multipolymers (EMAG), 4 kilograms of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymers (PTW), 0.8 kilogram of Vltra tears (HPMC) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 25 kilograms of ceramic fibers are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 138 |
| Notched Izod impact strength | J/M | ISO 180 | 134 |
| Flexural strength | MPa | ISO 178 | 227 |
| Modulus in flexure | MPa | ISO 178 | 11550 |
| Heat-drawn wire (1.82Mpa) | ℃ | ISO 75-1 | 206 |
| Density | g/cm 3 | ISO 1183 | 1.59 |
| Flame retardant properties | -- | UL-94 | 1.6V-0 |
Embodiment 5
1. by 36 kilograms of PBT resin, 1 kg of phosphoric acid ester coupling agent, 1 kilogram of silane coupling agent, 7 kilograms of organic hypophosphite, 6 kilograms of melamine polyphosphates, 4 kilograms of antimonous oxides, 3 kilograms of zinc borates, 1 kilogram of TAF, 1 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 1 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 4 kilograms of ethylene-methyl acrylate-glyceryl methacrylate multipolymers (EMAG), 4 kilograms of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymers (PTW), 1 kilogram of Vltra tears (HPMC) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 30 kilograms of ceramic fibers are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 154 |
| Notched Izod impact strength | J/M | ISO 180 | 157 |
| Flexural strength | MPa | ISO 178 | 249 |
| Modulus in flexure | MPa | ISO 178 | 13720 |
| Heat-drawn wire (1.82Mpa) | ℃ | ISO 75-1 | 211 |
| Density | g/cm 3 | ISO 1183 | 1.62 |
| Flame retardant properties | -- | UL-94 | 1.6V-0 |
Comparative example 1
1. by 77.2 kilograms of PBT resin, 0.1 kg of phosphoric acid ester coupling agent, 0.1 kilogram of silane coupling agent, 3 kilograms of organic hypophosphite, 3 kilograms of melamine polyphosphates, 2 kilograms of antimonous oxides, 2 kilograms of zinc borates, 0.2 kilogram of TAF, 0.1 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 0.1 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 1 kilogram of ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), 1 kilogram of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), 0.2 kilogram of Vltra tears (HPMC) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 15 kilograms of glass fibre are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 94 |
| Notched Izod impact strength | J/M | ISO 180 | 85 |
| Flexural strength | MPa | ISO 178 | 155 |
| Modulus in flexure | MPa | ISO 178 | 6550 |
| Heat-drawn wire 1.82MPa | ℃ | ISO 75-1 | 193 |
| Density | g/cm 3 | ISO 1183 | 1.40 |
| Flame retardant properties | -- | UL-94 | 3.2V-0 |
Comparative example 2
1. by 77.2 kilograms of PBT resin, 0.1 kg of phosphoric acid ester coupling agent, 0.1 kilogram of silane coupling agent, 3 kilograms of organic hypophosphite, 3 kilograms of melamine polyphosphates, 2 kilograms of antimonous oxides, 2 kilograms of zinc borates, 0.2 kilogram of TAF, 0.1 kilogram of β (3, 5-di-tert-butyl-hydroxy phenyl) propionate, 0.1 kilogram of tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 1 kilogram of ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), 1 kilogram of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW) mixes 3.5min in high-speed mixer,
2. the starting material of mixing are placed in the Strong shear twin screw extruder that length-to-diameter ratio is 40: 1, rotating speed is 350-450rpm through melt extruding, granulation, its expressing technique is 200 ~ 210 DEG C, a district, two 220 ~ 230 DEG C, districts, three 230 ~ 240 DEG C, districts, four 215 ~ 225 DEG C, districts, residence time 1-2 minute, pressure is 12-18Mpa;
3., in extrusion, 10 kilograms of ceramic fibers are evenly added by the accurate feed system metering of side direction, obtain the finished product after extruding tie rod, cooling, pelletizing, drying.
Test its performance by respective standard, be listed as follows:
| Test event | Unit | Testing standard | Test result |
| Tensile strength | MPa | ISO 527-2 | 93 |
| Notched Izod impact strength | J/M | ISO 180 | 84 |
| Flexural strength | MPa | ISO 178 | 135 |
| Modulus in flexure | MPa | ISO 178 | 6340 |
| Heat-drawn wire (1.82MPa) | ℃ | ISO 75-1 | 192 |
| Density | g/cm 3 | ISO 1183 | 1.40 |
| Flame retardant properties | -- | UL-94 | 3.2V-0 |
Following table is the performance data contrast of embodiment 1 and comparative example 1, comparative example 2:
Comparative example 1 is glass fibre as the contrast of material property during enhancement component and embodiment 1, drawn by correlation data: mechanical property and the flame retardant properties of adding ceramic fiber are obviously better than comparative example 1, it is better than adding the reinforced effects of glass fibre to PBT material that interpolation ceramic fiber is described; In addition, the glass fibre addition in comparative example 1 is 1.5 times of embodiment 1, draws thus, and when ceramic fiber does enhancement component as the addition needed for enhancement component than glass fibre, addition is few, therefore less on the impact of outward appearance.
Comparative example 2 is the contrasts without PBT material during dispersion agent and embodiment 1, drawn by correlation data: the reinforced effects without dispersion agent material constantly reduces greatly, visible dispersion agent plays a very important role the enhancement of ceramic fiber to PBT material, when without dispersion agent, ceramic fiber in the material dispersion effect is poor, has had a strong impact on reinforced effects.
Above the embodiment of the invention has been described in detail, but described content being only the preferred embodiment of the invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the invention scope change and improve, and all should still belong within this patent covering scope.
Claims (10)
1. ceramic fiber strengthens a flame-retardant PBT material, it is characterized in that:, be made up of following component by weight percentage:
2. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: the density of described PBT resin is 1.31 ~ 1.40g/cm3, fusing point 220 ~ 240 DEG C, and test condition is 230 DEG C, and standard test load is 2.16Kg.
3. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described ceramic fiber is the ceramic fiber of high temperature (HT) type, Fibre diameter 2 ~ 4 microns.
4. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described coupling agent component is: one or more in phosphate coupling agent, silane coupling agent, glycidyl ester.
5. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described fire retardant is one or more in organic hypophosphite, melamine polyphosphate, melamine cyanurate, antimonous oxide, sodium pyroantimoniate, zinc borate.
6. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described floating fine remover is TAF.
7. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described oxidation inhibitor is β (3,5-di-tert-butyl-hydroxy phenyl) propionate, two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, one or more in thio-2 acid 2 stearyl ester.
8. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described toughner is one in ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW) or its mixture.
9. ceramic fiber according to claim 1 strengthens flame-retardant PBT material, it is characterized in that: described dispersion agent is Vltra tears (HPMC), the one in polyacrylamide (PAM) or its mixture.
10. ceramic fiber according to claim 1 strengthens the preparation method of flame-retardant PBT material, it is characterized in that: concrete steps are as follows:
1) PBT, coupling agent, fire retardant, floating fine remover, oxidation inhibitor, toughner and dispersion agent are mixed 3.5min in high-speed mixer;
2) above-mentioned miscellany is added length-to-diameter ratio is 32: 1 ~ 40: 1, rotating speed is in the twin screw extruder of 350-450rpm, its expressing technique each district temperature range is 200 ~ 240 DEG C, residence time 1-2 minute, and pressure is 12-18Mpa;
3) in extrusion, ceramic fiber is evenly added by the accurate feed system metering of side direction, obtains the finished product after extruding tie rod, cooling, pelletizing, drying.
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Cited By (5)
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| CN105907055A (en) * | 2016-07-04 | 2016-08-31 | 蚌埠市正园电子科技有限公司 | Ceramic fiber reinforced PET material with epoxy resin adhesion and preparation method thereof |
| CN111087814A (en) * | 2019-10-09 | 2020-05-01 | 江苏集萃先进高分子材料研究所有限公司 | Battery pack box body refractory material and preparation method thereof |
| CN112280254A (en) * | 2020-07-27 | 2021-01-29 | 苏州市新广益电子有限公司 | Environment-friendly PBT home decoration film and adhesive tape produced by applying same |
| CN112724618A (en) * | 2020-12-29 | 2021-04-30 | 金旸（厦门）新材料科技有限公司 | Low-cost halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| US11364666B2 (en) | 2018-10-09 | 2022-06-21 | Shpp Global Technologies B.V. | Thermoplastic compositions having high stiffness and methods of making them |
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| CN112280254A (en) * | 2020-07-27 | 2021-01-29 | 苏州市新广益电子有限公司 | Environment-friendly PBT home decoration film and adhesive tape produced by applying same |
| CN112280254B (en) * | 2020-07-27 | 2023-06-02 | 苏州市新广益电子股份有限公司 | Environment-friendly PBT home decoration film and adhesive tape produced by using same |
| CN112724618A (en) * | 2020-12-29 | 2021-04-30 | 金旸（厦门）新材料科技有限公司 | Low-cost halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
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