CN102993651A - Glass-fiber-reinforced polybutylene terephthalate composite material and preparation method thereof - Google Patents
Glass-fiber-reinforced polybutylene terephthalate composite material and preparation method thereof Download PDFInfo
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- CN102993651A CN102993651A CN2012105400887A CN201210540088A CN102993651A CN 102993651 A CN102993651 A CN 102993651A CN 2012105400887 A CN2012105400887 A CN 2012105400887A CN 201210540088 A CN201210540088 A CN 201210540088A CN 102993651 A CN102993651 A CN 102993651A
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- polybutylene terephthalate
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Abstract
The invention discloses a glass-fiber-reinforced polybutylene terephthalate composite material and a preparation method thereof. The glass-fiber-reinforced polybutylene terephthalate composite material comprises the following raw materials: polybutylene terephthalate, glass fibers, a nucleating agent, mineral fillers and a toughening agent. According to the invention, by means of carrying out coating pretreatment on the glass fibers by the nucleating agent, the surface structure of the glass fibers is changed, the interaction between the glass fibers and a polybutylene terephthalate matrix is improved, the polybutylene terephthalate is induced to crystallize, the crystallinity of the polybutylene terephthalate is improved, and the morphological structure of a blend is changed. The glass-fiber-reinforced polybutylene terephthalate composite material provided by the invention has tensile strength ranging from 98MPa to 108MPa and impact strength ranging from 6.0KJ/m<2> to 6.6KJ/m<2>, and has the characteristics of simple preparation process, high crystallization rate, high crystallinity, good mechanical property, high surface gloss, low shrinkage factor, stable dimension and low warpage, and the production cost of the material is reduced while the comprehensive performance of the material is improved.
Description
Technical field
The present invention relates to glass reinforced plastics technical field, is a kind of glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material and preparation method thereof.
Background technology
As important engineering plastics, it is with physical mechanical and the electric property of excellence for polybutylene terephthalate (being called for short PBT), and the characteristics such as easy-formation processing are widely used in the fields such as electronic apparatus and automotive industry.
Along with developing rapidly of China's automobile industry, the energetically input of capital construction, also increasing to the demand of fiberglass reinforced engineering plastics.All need good comprehensive mechanical property and the engineering plastics of processing characteristics such as automobile door handle, air-conditioner air outlet etc.The polybutylene terephthalate (PBT) that glass strengthens is applied to automobile industry at present gradually.In recent years with Shanghai golden hair Development Co., Ltd (application number 200710046970.5), Pulite Composite Material Co., Ltd., Shanghai's (application number 200410017803.4), Rizhisheng New Technology Development Co., Ltd., Shanghai's (application number 200710170556.5) etc. research and develop it in succession for domestic many companies of representative, the patent of application is above 50 up to now, by compound respectively from anti-light aging, flame retardant resistance, thermotolerance, glossiness and warpage performance equal angles have solved the in a certain respect performance issue of automobile with the PBT material, but relevant PBT is surperficial, the lifting of the over-all properties such as mechanical property and processing characteristics is still waiting to improve.
Summary of the invention
The invention provides a kind of glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material and preparation method thereof, overcome the deficiency of above-mentioned prior art, make the matrix material of surface, mechanics and processing excellent combination property, satisfy the more and more higher requirement of automobile industry.
The invention provides a kind of glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material and preparation method thereof, overcome the deficiency of above-mentioned prior art, make the matrix material of surface, mechanics and processing excellent combination property, satisfy the more and more higher requirement of automobile industry.
One of technical scheme of the present invention realizes by following measures: a kind of glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material becomes 50 parts to 85 parts of polybutylene terephthalates, 10 parts to 30 parts in glass fibre, 0.01 part to 0.1 part of nucleator, 5 parts to 15 parts of mineral fillers, 0.1 part to 5 parts of toughner by the parts by weight of raw materials array; This glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material obtains in the steps below: the first step is added to the water the nucleator of aequum that to be made into mass percent concentration be 1% to 5% nucleator solution; Second step, the glass fibre of aequum is put into nucleator solution to be soaked, soak time is 1h to 5h, after the immersion soak solution and glass fibre being placed on temperature is that the water content of evaporating, being dried in the glass fibre under 60 ℃ to 100 ℃ is lower than 0.01%, obtains the glass fibre after nucleator coats; The 3rd step is with polybutylene terephthalate dry 2h to 6h under temperature is 100 ℃ to 140 ℃ of aequum; The 4th step, after high-speed mixer and mixing, add toughner and the mineral filler of dried polybutylene terephthalate, aequum in the twin screw extruder, polybutylene terephthalate, toughner and mineral filler add the glass fibre after nucleator coats in twin screw extruder after the melting in twin screw extruder, blending extrusion, cooling, pelletizing obtains glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material.
The below is the further optimization and/or improvements to one of foregoing invention technical scheme:
The limiting viscosity of above-mentioned polybutylene terephthalate is 0.8 dl/g to 1.2 dl/g; Or/and the fusing point of polybutylene terephthalate is 220 ℃ to 230 ℃.
Above-mentioned glass fibre is the glass fibre that process through silane coupling agent on the surface; Or/and the diameter of glass fibre is 9 μ m.
Above-mentioned nucleator is Sodium Benzoate, 1,3,2, more than one mixtures in the 4-dibenzylidene sorbitol.
Above-mentioned toughner is more than one mixtures in polyethylene-octene copolymer, the ethylene-propylene acid butyl ester-glycidyl methacrylate terpolymer.
The particle diameter of above-mentioned mineral filler is 100 order to 2500 orders.
Above-mentioned mineral filler is more than one mixtures in talcum powder, calcium carbonate, polynite, wilkinite, the vermiculite.
Above-mentioned polybutylene terephthalate, toughner and mineral filler are 2 minutes to 5 minutes in the high-speed mixer and mixing time.
The rotating speed of above-mentioned twin screw extruder is 80 r/min to 200 r/min; Or/and above-mentioned twin screw extruder barrel to the temperature of extrusion neck ring mold is 190 ℃ to 245 ℃.
Two of technical scheme of the present invention realizes by following measures: a kind of glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester composite manufacture method, carry out in the steps below: the first step is added to the water the nucleator of aequum that to be made into mass percent concentration be 1% to 5% nucleator solution; Second step, the glass fibre of aequum is put into nucleator solution to be soaked, soak time is 1h to 5h, after the immersion soak solution and glass fibre being placed on temperature is that the water content of evaporating, being dried in the glass fibre under 60 ℃ to 100 ℃ is lower than 0.01%, obtains the glass fibre after nucleator coats; The 3rd step is with polybutylene terephthalate dry 2h to 6h under temperature is 100 ℃ to 140 ℃ of aequum; The 4th step, after high-speed mixer and mixing, add toughner and the mineral filler of dried polybutylene terephthalate, aequum in the twin screw extruder, polybutylene terephthalate, toughner and mineral filler add the glass fibre after nucleator coats in twin screw extruder after the melting in twin screw extruder, blending extrusion, cooling, pelletizing obtains glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material; Wherein, this glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material becomes 50 parts to 85 parts of polybutylene terephthalates, 10 parts to 30 parts in glass fibre, 0.01 part to 0.1 part of nucleator, 5 parts to 15 parts of mineral fillers, 0.1 part to 5 parts of toughner by the parts by weight of raw materials array.
The below is two further optimization and/or improvements to the foregoing invention technical scheme:
Above-mentioned polybutylene terephthalate, toughner and mineral filler are 2 minutes to 5 minutes in the high-speed mixer and mixing time.
The rotating speed of above-mentioned twin screw extruder is 80 r/min to 200 r/min.
Above-mentioned twin screw extruder barrel to the temperature of extrusion neck ring mold is 190 ℃ to 245 ℃.
The limiting viscosity of above-mentioned polybutylene terephthalate is 0.8 dl/g to 1.2 dl/g; Or/and the fusing point of polybutylene terephthalate is 220 ℃ to 230 ℃.
Above-mentioned glass fibre is the glass fibre that process through silane coupling agent on the surface; Or/and the diameter of glass fibre is 9 μ m.
Above-mentioned nucleator is Sodium Benzoate, 1,3,2, more than one mixtures in the 4-dibenzylidene sorbitol.
Above-mentioned toughner is more than one mixtures in polyethylene-octene copolymer, the ethylene-propylene acid butyl ester-glycidyl methacrylate terpolymer.
The particle diameter of above-mentioned mineral filler is 100 order to 2500 orders.
Above-mentioned mineral filler is more than one mixtures in talcum powder, calcium carbonate, polynite, wilkinite, the vermiculite.
The present invention coats pre-treatment by glass fibre being carried out nucleator, changed the surface tissue of glass fibre, improved the interaction between glass fibre and the polybutylene terephthalate matrix, induce the polybutylene terephthalate crystallization, improve the degree of crystallinity of polybutylene terephthalate, changed the morphological structure of blend.The tensile strength of the glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material of gained of the present invention is 98 MPa to 108 MPa, and shock strength is 6.0 KJ/m
2To 6.6 KJ/m
2, have that preparation process is simple, crystallization rate is fast, degree of crystallinity is high, mechanical property is good, surface gloss is high, shrinking percentage is low, characteristics of dimensional stabilizing and low warpage, reduced production cost, improved over-all properties.
Description of drawings
Accompanying drawing 1 in the raw material not Added Nucleating Agents make control sample at the crystal habit structure iron under polarizing microscope behind the ultrathin section(ing).
Accompanying drawing 2 be to accompanying drawing 4 for sample of the present invention at the crystal habit structure iron under polarizing microscope behind the ultrathin section(ing).
Embodiment
The present invention is not subjected to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.
The invention will be further described below in conjunction with embodiment and accompanying drawing:
Embodiment 1, this glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material becomes 50 parts to 85 parts of polybutylene terephthalates, 10 parts to 30 parts in glass fibre, 0.01 part to 0.1 part of nucleator, 5 parts to 15 parts of mineral fillers, 0.1 part to 5 parts of toughner by the parts by weight of raw materials array.
Embodiment 2, this glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material becomes 5 parts of 0.01 part of 10 parts in 50 parts of polybutylene terephthalates or 85 parts, glass fibre or 30 parts, nucleator or 0.1 part, mineral fillers or 15 parts, 0.1 part or 5 parts of toughner by the parts by weight of raw materials array.
Embodiment 3, and this glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material becomes 59.99 parts of polybutylene terephthalates, 30 parts in glass fibre, 0.01 part of nucleator, 5 parts of mineral fillers, 5 parts of toughner by the parts by weight of raw materials array.
Embodiment 4, and this glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material becomes 59.9 parts of polybutylene terephthalates, 30 parts in glass fibre, 0.1 part of nucleator, 5 parts of mineral fillers, 5 parts of toughner by the parts by weight of raw materials array.
Embodiment 5, and as the optimization of above-described embodiment: the limiting viscosity of polybutylene terephthalate is 0.8 dl/g to 1.2 dl/g; Or/and the fusing point of polybutylene terephthalate is 220
oC to 230
oC.
Embodiment 6, are the glass fibre that process through silane coupling agent on the surface as the glass fibre of the optimization of above-described embodiment: embodiment 6; Or/and the diameter of glass fibre is 9 μ m.
Embodiment 7, are Sodium Benzoate as the nucleator of the optimization of above-described embodiment: embodiment 7; Perhaps nucleator is 1,3,2,4-dibenzylidene sorbitol; Perhaps nucleator is the mixture of Sodium Benzoate and 1,3,2,4-dibenzylidene sorbitol.
Embodiment 8, are polyethylene-octene copolymer as the toughner of the optimization of above-described embodiment: embodiment 8; Perhaps toughner is ethylene-propylene acid butyl ester-glycidyl methacrylate terpolymer; Perhaps toughner is the mixture of polyethylene-octene copolymer and ethylene-propylene acid butyl ester-glycidyl methacrylate terpolymer.
Embodiment 9, are 100 order to 2500 orders as the particle diameter of the mineral filler of the optimization of above-described embodiment: embodiment 9.
Embodiment 10, are more than one mixtures in talcum powder, calcium carbonate, polynite, wilkinite, the vermiculite as the mineral filler of the optimization of above-described embodiment: embodiment 10.
Embodiment 11, the glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester composite manufacture method of above-described embodiment 1 to embodiment 10, carry out in the steps below: the first step is added to the water the nucleator of aequum that to be made into mass percent concentration be 1% to 5% nucleator solution; Second step, the glass fibre of aequum is put into nucleator solution to be soaked, soak time is 1h to 5h, after the immersion soak solution and glass fibre being placed on temperature is that the water content of evaporating, being dried in the glass fibre under 60 ℃ to 100 ℃ is lower than 0.01%, obtains the glass fibre after nucleator coats; The 3rd step is with polybutylene terephthalate dry 2h to 6h under temperature is 100 ℃ to 140 ℃ of aequum; The 4th step, after high-speed mixer and mixing, add toughner and the mineral filler of dried polybutylene terephthalate, aequum in the twin screw extruder, polybutylene terephthalate, toughner and mineral filler add the glass fibre after nucleator coats in twin screw extruder after the melting in twin screw extruder, blending extrusion, cooling, pelletizing obtains glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material.
Embodiment 12, the glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester composite manufacture method of above-described embodiment 1 to embodiment 10, carry out in the steps below: the first step is added to the water the nucleator of aequum that to be made into mass percent concentration be 1% or 5% nucleator solution; Second step, the glass fibre of aequum is put into nucleator solution to be soaked, soak time is 1h or 5h, after the immersion soak solution and glass fibre being placed on temperature is that the water content of evaporating, being dried in the glass fibre under 60 ℃ or 100 ℃ is lower than 0.01%, obtains the glass fibre after nucleator coats; The 3rd step was 100 ℃ or 140 ℃ of lower dry 2h or 6h with the polybutylene terephthalate of aequum in temperature; The 4th step, after high-speed mixer and mixing, add toughner and the mineral filler of dried polybutylene terephthalate, aequum in the twin screw extruder, polybutylene terephthalate, toughner and mineral filler add the glass fibre after nucleator coats in twin screw extruder after the melting in twin screw extruder, blending extrusion, cooling, pelletizing obtains glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material.
Embodiment 13, are 2 minutes to 5 minutes as polybutylene terephthalate, toughner and the mineral filler of the optimization of above-described embodiment: embodiment 13 in the high-speed mixer and mixing time.
Embodiment 14, are 80 r/min to 200 r/min as the rotating speed of the twin screw extruder of the optimization of above-described embodiment: embodiment 14.
Embodiment 15, are 190 ℃ to 245 ℃ as the twin screw extruder barrel of the optimization of above-described embodiment: embodiment 15 and the temperature of extrusion neck ring mold.
After the glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material of above-described embodiment gained places the convection oven drying, adopt the injection moulding machine injection moulding to make sample of the present invention; In the raw material not Added Nucleating Agents make control sample; The average behaviour parameter of sample of the present invention and control sample is as shown in table 1:
Table 1
| Sample of the present invention | Control sample | |
| Tensile strength (MPa) | 98 to 108 | 69 to 95 |
| Modulus in flexure (MPa) | 6431 to 6859 | 3560 to 7100 |
| Shock strength (KJ/m 2） | 6.0 to 6.6 | 2.8 to 5.6 |
| Degree of crystallinity (%) | 42.7 to 48.3 | 35.4 to 36.8 |
| Crystallization rate-flexible chain (s) | 4.14 to 5.05 | 8.13 to 8.94 |
| Surface quality | Well | Generally |
The tensile property test of injection moulding sample is according to the GB/T1040.1-2006 standard testing, and rate of extension is 10 mm/min; The bending property test is according to GB/T 9341-2008 standard testing, and crooked speed is 2 mm/min; The notched Izod impact strength test is according to GB/T 1843-2008 standard testing, and v-notch, pendulum energy are 5.5 J.The degree of crystallinity of injection moulding sample and crystallization rate adopt differential scanning calorimeter to test, and temperature rise rate is 10
oC/min, rate of temperature fall are 20
oC/min; The crystal habit of polarized light microscope observing PBT.The surface quality of injected sample (surface gloss, warpage degree) is observed the specimen size that adopts: diameter is 50 mm, and thickness is 2 mm, and it mainly is divided into: " good, general, relatively poor " Three Estate.
As can be seen from Table 1, the tensile strength of sample of the present invention, modulus in flexure, shock strength, degree of crystallinity, crystallization rate-flexible chain and surface quality are respectively 98 MPa to 108 MPa, 6431 MPa to 6859 MPa, 6.0 KJ/m
2To 6.6 KJ/m
2, 42.7% to 48.3%, 4.14 s to 5.05 s, good; The tensile strength of control sample, modulus in flexure, shock strength, degree of crystallinity, crystallization rate (flexible chain) and surface quality are respectively 69 MPa to 95 MPa, 3560 MPa to 7100 MPa, 2.8 KJ/m
2To 5.6 KJ/m
2, 35.4% to 36.8%, 8.13 s to 8.94 s, general; Sample of the present invention all be improved than tensile strength, modulus in flexure, shock strength, degree of crystallinity and the surface quality of control sample and crystallization rate fast.So glass fibre can improve the mechanical property of polybutylene terephthalate (PBT) effectively, but too much glass fibre can affect polybutylene terephthalate (PBT) composite material surface quality; And an amount of mineral filler can obtain to obtain on the basis of certain mechanical property the reduction of production cost; And the introducing of nucleator improves degree of crystallinity and the crystallization rate of system effectively, thereby has obtained effective improvement of mechanical property.
Can further learn 4 from accompanying drawing 1 to accompanying drawing: crystal grain of the present invention is less, shows that nucleator has played nucleogenesis, has improved crystallization rate.
Above technical characterictic has consisted of embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease according to actual needs non-essential technical characterictic, satisfies the demand of different situations.
Claims (10)
1. a glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material is characterized in that becoming 50 parts to 85 parts of polybutylene terephthalates, 10 parts to 30 parts in glass fibre, 0.01 part to 0.1 part of nucleator, 5 parts to 15 parts of mineral fillers, 0.1 part to 5 parts of toughner by the parts by weight of raw materials array; This glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material obtains in the steps below: the first step is added to the water the nucleator of aequum that to be made into mass percent concentration be 1% to 5% nucleator solution; Second step, the glass fibre of aequum is put into nucleator solution to be soaked, soak time is 1h to 5h, after the immersion soak solution and glass fibre being placed on temperature is that the water content of evaporating, being dried in the glass fibre under 60 ℃ to 100 ℃ is lower than 0.01%, obtains the glass fibre after nucleator coats; The 3rd step is with polybutylene terephthalate dry 2h to 6h under temperature is 100 ℃ to 140 ℃ of aequum; The 4th step, after high-speed mixer and mixing, add toughner and the mineral filler of dried polybutylene terephthalate, aequum in the twin screw extruder, polybutylene terephthalate, toughner and mineral filler add the glass fibre after nucleator coats in twin screw extruder after the melting in twin screw extruder, blending extrusion, cooling, pelletizing obtains glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material.
2. glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material according to claim 1, the limiting viscosity that it is characterized in that polybutylene terephthalate is 0.8 dl/g to 1.2d dl/g; Or/and the fusing point of polybutylene terephthalate is 220 ℃ to 230 ℃.
3. glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material according to claim 1 and 2 is characterized in that glass fibre is the glass fibre that process through silane coupling agent on the surface; Or/and the diameter of glass fibre is 9 μ m.
4. according to claim 1 and 2 or 3 described glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix materials, it is characterized in that nucleator is Sodium Benzoate, 1,3,2, more than one mixtures in the 4-dibenzylidene sorbitol.
5. according to claim 1 and 2 or 3 or 4 described glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix materials, it is characterized in that toughner is more than one mixtures in polyethylene-octene copolymer, the ethylene-propylene acid butyl ester-glycidyl methacrylate terpolymer.
6. according to claim 1 and 2 or 3 or 4 or 5 described glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix materials, the particle diameter that it is characterized in that mineral filler is 100 order to 2500 orders.
7. according to claim 1 and 2 or 3 or 4 or 5 or 6 described glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix materials, it is characterized in that mineral filler is more than one mixtures in talcum powder, calcium carbonate, polynite, wilkinite, the vermiculite.
8. glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester composite manufacture method according to claim 17, it is characterized in that carrying out in the steps below: the first step is added to the water the nucleator of aequum that to be made into mass percent concentration be 1% to 5% nucleator solution; Second step, the glass fibre of aequum is put into nucleator solution to be soaked, soak time is 1h to 5h, after the immersion soak solution and glass fibre being placed on temperature is that the water content of evaporating, being dried in the glass fibre under 60 ℃ to 100 ℃ is lower than 0.01%, obtains the glass fibre after nucleator coats; The 3rd step is with polybutylene terephthalate dry 2h to 6h under temperature is 100 ℃ to 140 ℃ of aequum; The 4th step, after high-speed mixer and mixing, add toughner and the mineral filler of dried polybutylene terephthalate, aequum in the twin screw extruder, polybutylene terephthalate, toughner and mineral filler add the glass fibre after nucleator coats in twin screw extruder after the melting in twin screw extruder, blending extrusion, cooling, pelletizing obtains glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material.
9. glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester composite manufacture method according to claim 8 is characterized in that polybutylene terephthalate, toughner and mineral filler are 2 minutes to 5 minutes in the high-speed mixer and mixing time.
10. according to claim 8 or 9 described glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester composite manufacture methods, the rotating speed that it is characterized in that twin screw extruder is 80 r/min to 200 r/min; Or/and twin screw extruder barrel to the temperature of extrusion neck ring mold is 190 ℃ to 245 ℃.
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| CN104151789A (en) * | 2014-07-16 | 2014-11-19 | 厦门金越电器有限公司 | Low-warping high voltage resistance PBT modified material and preparation method thereof |
| CN106009539A (en) * | 2016-06-22 | 2016-10-12 | 西华大学 | Polymer material containing flame retardant adopting gradient concentration distribution |
| CN110669320A (en) * | 2019-08-26 | 2020-01-10 | 天津柯文实业股份有限公司 | Preparation method of high-impact-resistance high-low-temperature-resistance poly (p-xylylene glycol terephthalate) |
| CN110922680A (en) * | 2019-11-15 | 2020-03-27 | 江苏东方电缆材料有限公司 | Basalt fiber reinforced and toughened polypropylene-based composite material and preparation method thereof |
| CN111621125A (en) * | 2020-06-17 | 2020-09-04 | 宁波华腾首研新材料有限公司 | High-performance enhanced halogen-free red-phosphorus-free flame-retardant PBT (polybutylene terephthalate) engineering plastic material and preparation method thereof |
| CN111995843A (en) * | 2020-08-24 | 2020-11-27 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polybutylene terephthalate composite material and preparation method thereof |
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| CN104151789A (en) * | 2014-07-16 | 2014-11-19 | 厦门金越电器有限公司 | Low-warping high voltage resistance PBT modified material and preparation method thereof |
| CN104151789B (en) * | 2014-07-16 | 2016-10-05 | 厦门金越电器有限公司 | A kind of low warpage, high pressure PBT modification class material and preparation method thereof |
| CN106009539A (en) * | 2016-06-22 | 2016-10-12 | 西华大学 | Polymer material containing flame retardant adopting gradient concentration distribution |
| CN106009539B (en) * | 2016-06-22 | 2018-04-20 | 西华大学 | A kind of high molecular material of flame retardant concentration gradient distribution and preparation method thereof |
| CN110669320A (en) * | 2019-08-26 | 2020-01-10 | 天津柯文实业股份有限公司 | Preparation method of high-impact-resistance high-low-temperature-resistance poly (p-xylylene glycol terephthalate) |
| CN110922680A (en) * | 2019-11-15 | 2020-03-27 | 江苏东方电缆材料有限公司 | Basalt fiber reinforced and toughened polypropylene-based composite material and preparation method thereof |
| CN111621125A (en) * | 2020-06-17 | 2020-09-04 | 宁波华腾首研新材料有限公司 | High-performance enhanced halogen-free red-phosphorus-free flame-retardant PBT (polybutylene terephthalate) engineering plastic material and preparation method thereof |
| CN111621125B (en) * | 2020-06-17 | 2022-02-01 | 宁波华腾首研新材料有限公司 | High-performance enhanced halogen-free red-phosphorus-free flame-retardant PBT (polybutylene terephthalate) engineering plastic 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 |
| 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 |
| CN111995843A (en) * | 2020-08-24 | 2020-11-27 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polybutylene terephthalate composite material and preparation method thereof |
| CN112778715A (en) * | 2020-12-30 | 2021-05-11 | 广东顺德顺炎新材料股份有限公司 | Modified PBT (polybutylene terephthalate) material suitable for thermal sublimation transfer printing and preparation method thereof |
| CN114213818A (en) * | 2022-01-20 | 2022-03-22 | 中国科学院兰州化学物理研究所 | Polybutylene terephthalate-based bridge support friction material and preparation method thereof |
| CN114213818B (en) * | 2022-01-20 | 2023-01-17 | 中国科学院兰州化学物理研究所 | Polybutylene terephthalate-based bridge support friction material and preparation method thereof |
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Application publication date: 20130327 |