CN1580122A - Method for preparing high surface finish glass fiber reinforced polyester composite material - Google Patents
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Abstract
This invention refers to a kind of composite of glass fiber strengthened polyester with high surface smoothness and is composed of between 45% and 80% of polyester, between1% and 8% of surface modifier, between 0.5% and 3.5% of nucleater, between 1.0% and 5% of toughening and chain-entendig agent, between 0.1% and 1% of antioxidant and between 10% and 50% of fiber glass. The manufacturing method chooses the polyester as the matrix, adds the surface modifier, surface modifier, toughening and chain-entendig agent, antioxidant and fiber glass, melts, extrudes and granulates them. The invention is featured by the simple manufacturing method, low cost, high surface smoothness and good mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of high surface finish glass-fiber-reinforced polyester matrix material, can be used for the engineering plastics field, belong to technical field of polymer materials.
Background technology
Linear saturated polyester such as PET, PBT etc. have just obtained gyp application a long time ago as the high-quality raw material of fiber, film and other various goods.Since its excellent physics and chemical property, particularly in recent years, the perfect and development of technology such as relevant crystallization nucleation, they are applied in the engineering plastics field more and more.Glass-fiber-reinforced polyester by correlation technique can so that glass fibre and polyester be able to closely compound, thereby improve the mechanical property of material and other physicalies greatly, also improved the thermal property and the machine-shaping property of material simultaneously.Machine-shaping property by these technology preparations is good, the glass-fiber-reinforced polyester of the every mechanical property excellence of material has obtained to use more widely with its more excellent cost performance.
Yet the same with other glass fibre reinforcements, along with the increase of content of glass fiber in the importing of glass fibre, particularly system, worsening appears in the product surface appearance that makes of material thereupon thus.Expose to the coarse relatively glass fibre in product surface and destroyed the slickness and the glossiness on product surface.The goods that the generation of this phenomenon is had relatively high expectations for surface quality, as fascia, exterior trimming parts etc., unless the processing of additional special surface treatment of process or material, otherwise be to be difficult to accept.For this reason, this owing to glass fibre exposes the phenomenon that causes the product apparent mass to worsen in order to solve, people have done a large amount of research and inquirement.
Fedell, et al. is at USP.35, proposed in 984 to use a kind of fibrous body fineness at 1 micron with interior glass fibre, can be by the uniform distribution of this kind fiber in resin so that by the prepared material that comes out of this kind method, product surface flatness and glossiness all reach a perfect condition.And inquired into this microfibre and how in resin, to have realized distributing uniformly.
Hiromichi and Tetsuji have also mentioned in JP.60-21947 and have used the fine glass fibre of length-to-diameter ratio in an OK range to improve the method for material product apparent mass as fortifying fibre.
Fujii etc. in USP.6191207, then propose this its requirement of glass fibre that can improve the bill of material appearance quality must reach the main body fineness at 15～30 microns, footpath than in 10～20 scope.
Ushiroji, et al. has proposed the system of the superoxide of a kind of 25～65 parts ethylene-propylene rubber(EPR), 75～35 parts thermoplastic resin, 10～100 parts glass fibre, 0.5～5 part maleic anhydride inoculated polypropylene and 0.02～0.5 part in USP.4912150, the bill of material appearance quality problem prepared by this system also obtained solution.
Park, et al. have also proposed in USP.5731375 with the method for a kind of elastomer copolymer as apparent mass properties-correcting agent.
Yoshimura, et al. have then proposed to use a kind of rare-earth mineral component in USP.4528304, also can be so that the apparent mass problem of material is resolved by introduce this kind component in the fibreglass reinforced thermoplastic system.
Schell; The patented technology USP.5804313 of Philip L. has introduced a kind of method of in advance fiberglass surfacing being carried out the processing of special resin coating.The apparent mass of the glass fibre reinforcement after handling in this way is also very desirable.
The technology that above-mentioned these patents provided has solved glass fibre from different angles and has exposed the product apparent mass deterioration problem that is caused.Yet, can find out obviously that also all also there is its weak point in these patented technologies.They otherwise the raw material for preparing these glass fibre reinforced composions proposed a lot of special requirements, as USP.35,984, the fine glass fibre of the special fineness mentioned among JP.60-21947, the USP.6191207; Handle as the special surface coating of mentioning among the USP.5804313; As rare-earth mineral component of mentioning among the USP.4528304 etc., thereby will obviously cause the significantly rising of product cost; They are as cost with the mechanics of sacrificing certain glass fibre reinforcement excellence and thermal property, as the elastomeric use that proposes among USP.4912150, the USP.5731375, though therefrom can obtain the corresponding good apparent mass of product, the mechanical property of material and thermal property inevitably are subjected to greater loss.Therefore, for some had both required material that good mechanics and thermal property are arranged like this such as fascia, exterior trimming parts etc., require simultaneously the product of apparent mass excellence again, how to make original these mechanics of product and thermal property not suffer damage, can guarantee simultaneously the apparent mass of goods again, and the also therefore significantly rising of the production preparation cost of material, remain a problem that difficulty is very big.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation technology is simple, cost is low, the preparation method of the high surface finish glass-fiber-reinforced polyester matrix material of excellent performance.
For realizing above purpose, technical scheme of the present invention provides a kind of high surface finish glass-fiber-reinforced polyester matrix material, and its characteristics are, add surface-modifying agent, and it is mixed with by following materials of weight proportions: (%)
Polyester 45-80
Surface-modifying agent 1-8
Nucleator 0.5-3.5
Toughness reinforcing, chainextender 1.0-5
Oxidation inhibitor 0.1-1
Glass fibre 10-50
Described polyester is a relative density 1.35～1.38,255～260 ℃ of fusing points, the polyethylene terephthalate of melt viscosity 0.3～1.0 or relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.3～1.0; Described surface-modifying agent is the polyoxyethylene wax that contains carbonyl functional group of molecular weight between 1000～20000; Described nucleator is a relative density 1.14～1.15, nylon 6 that fusing point is 215～225 ℃ or relative density 1.10～1.15, nylon 66 that fusing point is 238～248 ℃ or relative density 2.7～2.8, the talcum powder of order several 1250～2500; Described toughness reinforcing, chainextender is a kind of ethylene copolymer that contains epoxy-functional, can be the graft copolymer of the glyceryl ester of ethylene-propylene rubber(EPR) and methacrylic; Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, or three (2, the 4-di-tert-butylphenol) phosphorous acid ester; Described glass fiber diameter is the 6-17 micron.
A kind of preparation method of high surface finish glass-fiber-reinforced polyester matrix material, its method is as follows:
(1) weighs raw material by weight ratio;
(2) glass fibre is handled through silane coupling agent KH550, diameter is the 6-17 micron; Silane coupling agent KH550 chemical name is a γ-An Bingjisanyiyangjiguiwan;
(3) polyester, surface-modifying agent, nucleator, toughness reinforcing, chainextender, oxidation inhibitor are done in super mixer and mixed 3-5 minute;
(4) raw materials mixed is placed dual-screw-stem machine with the glass fibre blending, through melt extruding, granulation, its technology is: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
The present invention adopts the properties-correcting agent of a kind of carbonyl functional group's of containing polyoxyethylene wax as the surface flatness and the glossiness of glass-fiber-reinforced polyester material, can make the surface exposed glass fibre of product be able to good covering by this properties-correcting agent, reach and improve glass-fiber-reinforced polyester product surface, make it have the purpose of best bright finish.In addition, this properties-correcting agent can also play certain compatibilization to the glass-fiber-reinforced polyester material when addition reaches certain proportion, thereby produce the apparent mass excellence, can also overcome simultaneously original mechanics of material that prior art caused at the apparent mass that improves glass-fiber-reinforced polyester simultaneously and the shortcoming that thermal property is undermined and cost raises up.
Advantage of the present invention is:
1, the present invention has used apparent mass properties-correcting agent efficiently, the surface flatness of obtained matrix material and glossiness excellence, and this surface-modifying agent has certain compatibilization effect simultaneously, and other performances of material are had no adverse effect.
2, the present invention has used effective toughness reinforcing, chainextender and crystallization nucleating agent in the glass-fiber-reinforced polyester matrix material, and prepared matrix material has characteristics such as easy processing, high-impact, intensity and modulus height.
3, the present invention adopts cheap commercially available organism as components such as surface-modifying agent, nucleator, toughness reinforcing, chainextender and oxidation inhibitor, has reduced production cost of products.
4, the preparation technology of the glass-fiber-reinforced polyester matrix material of the present invention's proposition is simple, cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In the embodiment composite-material formula, polyester is a relative density 1.35～1.38,255～260 ℃ of fusing points, the polyethylene terephthalate PET of melt viscosity 0.3～1.0 or relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate PBT of melt viscosity 0.3～1.0; Surface-modifying agent is the polyoxyethylene wax that contains carbonyl functional group of molecular weight between 1000～20000; Nucleator is a relative density 2.7～2.8, the talcum powder of order several 1250～2500; Toughness reinforcing, chainextender is a kind of ethylene copolymer that contains epoxy-functional, and the trade names of producing as U.S. Dupont company are the multipolymer of Elvaloy PTW; Glass fibre is handled through silane coupling agent KH550, and diameter is the 6-17 micron, and wherein silane coupling agent KH550 chemical name is a γ-An Bingjisanyiyangjiguiwan; The oxidation inhibitor chemical name is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, produces as Ciba company, and trade names are Irganox 1010.
Embodiment 1
With the PET weight ratio be 63.4%, polyoxyethylene 2%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, melt extrude through 260～280 ℃, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Embodiment 2
With the PET weight ratio be 61.4%, polyoxyethylene 4%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extruding, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Embodiment 3
With the PET weight ratio be 59.4%, polyoxyethylene 6%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extruding, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Embodiment 4
With the PBT weight ratio be 63.4%, polyoxyethylene 2%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, melt extrude through 230～240 ℃, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Embodiment 5
With the PBT weight ratio be 61.4%, polyoxyethylene 4%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, melt extrude through 230～240 ℃, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Embodiment 6
With the PBT weight ratio be 59.4%, polyoxyethylene 6%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, melt extrude through 230～240 ℃, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 260 ℃ in a district, 265 ℃ in two districts, 270 ℃ in three districts, 265 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Comparative Examples 1
With the PET weight ratio be 65.4%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extruding, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Comparative Examples 2
With the PBT weight ratio be 65.4%, talcum powder 2%, PTW2.5% and 1010,0.1% did under room temperature state mixed 4 minutes in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extruding, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 245 ℃ in a district, 250 ℃ in two districts, 250 ℃ in three districts, 245 ℃ in four districts; The residence time is 1 minute, and pressure is 12Mpa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 120～140 ℃ convection oven dry 4～8 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection moulding machine.The injection mold temperature control is about 100 ℃.
The tensile property test is undertaken by ISO 527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 55*6*4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO 75, and specimen size is 127*12.7*3.2mm, and load is 1.82MPa.
Comprehensive mechanical performance is passed through the tensile strength of test gained, elongation at break, and the numerical value of modulus in flexure and shock strength is passed judgment on; The crystallization nucleation performance of material is passed judgment on by the size of the heat-drawn wire of test gained; The apparent mass of material characterizes by self-defining " micro-clouding and a large amount of clouding, a small amount of clouding, smooth, glossy " four grades according to the slickness and the glossiness on model surface.
The prescription of embodiment 1-6 and Comparative Examples 1-2 and every The performance test results be each table as follows:
Table 1 high surface finish glass fibre REINFORCED PET composite-material formula and material property table
| The matrix material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| ????PET(％) | ????63.4 | ????61.4 | ????59.4 | ????65.4 |
| Surface-modifying agent | ????2 | ????4 | ????6 | ????- |
| Talcum powder (%) | ????2 | ????2 | ????2 | ????2 |
| ????PTW(％) | ????2.5 | ????2.5 | ????2.5 | ????2.5 |
| ????1010(％) | ????0.1 | ????0.1 | ????0.1 | ????0.1 |
| Glass fibre (%) | ????30 | ????30 | ????30 | ????30 |
| Heat-drawn wire (1.82MPa) (℃) | ????225 | ????228 | ????205 | ????224 |
| Unnotched impact strength (kJ/m 2) | ????25 | ????30 | ????28 | ????22 |
| Tensile strength (MPa) | ????162 | ????165 | ????145 | ????162 |
| Elongation at break (%) | ????3.2 | ????3.2 | ????4.5 | ????3.0 |
| Modulus in flexure (MPa) | ????11270 | ????125000 | ????9800 | ????11000 |
| Apparent mass | A small amount of clouding | Smooth, glossy | The trace clouding | A large amount of cloudings |
Last table shows that it is right to use polyoxyethylene to play in the matrix material of glass fibre REINFORCED PET
The effect that the goods apparent mass improves.Comparative example 1,2,3 and Comparative Examples 1 are as can be known, when the polyoxyethylene consumption is between 2～4 parts, the effect that this apparent mass improves is best, and the tensile strength of material and the not only not reduction of thermal properties such as modulus in flexure, extension at break and heat-drawn wire, slightly improves on the contrary.This has illustrated that also polyoxyethylene not only can play the effect of a surface-modifying agent simultaneously, and has played the compatibilization to system, make that combination must be tightr between glass fibre and the resin, thereby every performance has all had certain raising.But the usage quantity of polyoxyethylene can not be too high in the system, improve if too high not only bill of material appearance quality obtains ideal, and reduction in various degree all appears in other mechanical properties and thermal property.
Table 2 high surface finish glass fibre strengthens PBT composite-material formula and material property table
| The matrix material title | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 2 |
| ????PBT(％) | ????63.4 | ????61.4 | ????59.4 | ????65.4 |
| Surface-modifying agent | ????2 | ????4 | ????6 | ????- |
| Talcum powder (%) | ????2 | ????2 | ????2 | ????2 |
| ????PTW(％) | ????2.5 | ????2.5 | ????2.5 | ????2.5 |
| ????1010(％) | ????0.1 | ????0.1 | ????0.1 | ????0.1 |
| Glass fibre (%) | ????30 | ????30 | ????30 | ????30 |
| Heat-drawn wire (1.82MPa) (℃) | ????210 | ????214 | ????190 | ????208 |
| Unnotched impact strength (kJ/m 2) | ????31 | ????35 | ????30 | ????30 |
| Tensile strength (MPa) | ????155 | ????158 | ????134 | ????153 |
| Elongation at break (%) | ????3.5 | ????3.6 | ????5.0 | ????3.0 |
| Modulus in flexure (MPa) | ????9500 | ????9600 | ????7900 | ????9200 |
| Apparent mass | A small amount of clouding | Smooth, glossy | The trace clouding | A large amount of cloudings |
Last table shows equally, uses polyoxyethylene can play the effect that the goods apparent mass is improved in the matrix material of glass fibre enhancing PBT.Comparative example 4,5,6 and Comparative Examples 2 are as can be known, when the polyoxyethylene consumption is between 2～4 parts, the effect that this apparent mass improves is best, and the tensile strength of material and the not only not reduction of thermal properties such as modulus in flexure, extension at break and heat-drawn wire, slightly improves on the contrary.This has illustrated that also polyoxyethylene not only can play the effect of a surface-modifying agent simultaneously, and has played the compatibilization to system, make that combination must be tightr between glass fibre and the resin, thereby every performance has all had certain raising.But the usage quantity of polyoxyethylene can not be too high in the system, improve if too high not only bill of material appearance quality obtains ideal, and reduction in various degree all appears in other mechanical properties and thermal property.
Claims (8)
1. a high surface finish glass-fiber-reinforced polyester matrix material is characterized in that, adds surface-modifying agent, and it is mixed with by following materials of weight proportions: (%)
Polyester 45-80
Surface-modifying agent 1-8
Nucleator 0.5-3.5
Toughness reinforcing, chainextender 1.0-5
Oxidation inhibitor 0.1-1
Glass fibre 10-50
2. a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1, it is characterized in that, described polyester is a relative density 1.35～1.38,255～260 ℃ of fusing points, the polyethylene terephthalate of melt viscosity 0.3～1.0 or relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.3～1.0.
3. a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1 is characterized in that, described surface-modifying agent is the polyoxyethylene wax that contains carbonyl functional group of molecular weight between 1000～20000.
4. a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1, it is characterized in that, described nucleator is a relative density 1.14～1.15, nylon 6 that fusing point is 215～225 ℃ or relative density 1.10～1.15, nylon 66 that fusing point is 238～248 ℃ or relative density 2.7～2.8, the talcum powder of order several 1250～2500.
5. a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1, it is characterized in that, described toughness reinforcing, chainextender is a kind of ethylene copolymer that contains epoxy-functional, can be the graft copolymer of the glyceryl ester of ethylene-propylene rubber(EPR) and methacrylic.
6. a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1, it is characterized in that described oxidation inhibitor is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, or three (2, the 4-di-tert-butylphenol) phosphorous acid ester.
7. a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1 is characterized in that described glass fiber diameter is the 6-17 micron.
8. the preparation method of a kind of high surface finish glass-fiber-reinforced polyester matrix material according to claim 1 is characterized in that, its method is as follows:
(1) weighs raw material by weight ratio;
(2) glass fibre is handled through silane coupling agent KH550, diameter is the 6-17 micron; Silane coupling agent KH550 chemical name is a γ-An Bingjisanyiyangjiguiwan;
(3) polyester, surface-modifying agent, nucleator, toughness reinforcing, chainextender, oxidation inhibitor are done in super mixer and mixed 3-5 minute;
(4) raw materials mixed is placed dual-screw-stem machine with the glass fibre blending, through melt extruding, granulation, its technology is: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
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| CN101070421B (en) * | 2006-12-22 | 2010-09-08 | 深圳市科聚新材料有限公司 | High-heat-resisting glass-fiber reinforced polyester composite material and preparing method |
| CN101906251A (en) * | 2009-06-04 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Composite material for wind power generator blade and preparation method thereof |
| CN101134839B (en) * | 2007-09-30 | 2011-01-12 | 深圳市科聚新材料有限公司 | Flame-proof glass fibre reinforced polycarbonate material and method for making same |
| CN103146154A (en) * | 2011-12-07 | 2013-06-12 | 上海杰事杰新材料(集团)股份有限公司 | PET composite material, preparation method and application thereof |
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| CN101070421B (en) * | 2006-12-22 | 2010-09-08 | 深圳市科聚新材料有限公司 | High-heat-resisting glass-fiber reinforced polyester composite material and preparing method |
| CN101134839B (en) * | 2007-09-30 | 2011-01-12 | 深圳市科聚新材料有限公司 | Flame-proof glass fibre reinforced polycarbonate material and method for making same |
| CN101906251A (en) * | 2009-06-04 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Composite material for wind power generator blade and preparation method thereof |
| CN101906251B (en) * | 2009-06-04 | 2013-06-12 | 上海杰事杰新材料(集团)股份有限公司 | Composite material for wind power generator blade and preparation method thereof |
| CN103146154A (en) * | 2011-12-07 | 2013-06-12 | 上海杰事杰新材料(集团)股份有限公司 | PET composite material, preparation method and application thereof |
| CN103146154B (en) * | 2011-12-07 | 2016-12-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of PET composite material, preparation method and applications |
| CN103304965A (en) * | 2012-03-13 | 2013-09-18 | 合肥杰事杰新材料股份有限公司 | Polybutylene terephthalate (PBT) composition and preparation method thereof |
| CN103304965B (en) * | 2012-03-13 | 2016-12-14 | 合肥杰事杰新材料股份有限公司 | A kind of polybutylene terephthalate compositions and preparation method thereof |
| CN103709681A (en) * | 2013-12-20 | 2014-04-09 | 上海日之升新技术发展有限公司 | High-toughness and high-heatproof glass fiber reinforced PBT (Polybutylece Terephthalate) composite material and preparation method thereof |
| CN103709681B (en) * | 2013-12-20 | 2016-03-30 | 上海日之升新技术发展有限公司 | A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof |
| CN109844022A (en) * | 2016-10-14 | 2019-06-04 | 三井化学株式会社 | Resin combination and formed body |
| CN109844022B (en) * | 2016-10-14 | 2021-10-29 | 三井化学株式会社 | Resin composition and molded article |
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