CN100519653C - Fiberglass enhanced PCT composite material in high flowing property - Google Patents
Fiberglass enhanced PCT composite material in high flowing property Download PDFInfo
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- CN100519653C CN100519653C CNB2004100178049A CN200410017804A CN100519653C CN 100519653 C CN100519653 C CN 100519653C CN B2004100178049 A CNB2004100178049 A CN B2004100178049A CN 200410017804 A CN200410017804 A CN 200410017804A CN 100519653 C CN100519653 C CN 100519653C
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- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000011152 fibreglass Substances 0.000 title description 2
- 239000003365 glass fiber Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 44
- 239000011159 matrix material Substances 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 26
- -1 pentaerythritol ester Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
- 229920001038 ethylene copolymer Polymers 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 49
- 230000008569 process Effects 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000005453 pelletization Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 22
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000007822 coupling agent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000004927 fusion Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003314 Elvaloy® Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A glass fibre reinforced PBT composite is prepared from PBT, flowing promoter, flexibilizing compatilizer, antioxygen and glass fibre. Its preparing process includes using PBT as base body; adding antioxygen, flowing promoter and flexibilizing compatibilizer on base body; melting and extruding prepared material with glass fibre and then pelletizing.
Description
Technical field
The matrix material of the glass-fiber-reinforced polyester of a kind of high workability energy of the present invention relates to polymer composite and preparation method thereof., relate to more specifically that a kind of technology is easy, with low cost, the high workability that is suitable for the moulding of complex structure large-scale thin wall parts can glass fibre strengthen the matrix material of PBT.
Background technology
Because the component that adopt glass fibre to strengthen the PBT material preparation can obtain good thermotolerance, flame retardant resistance, electric insulating quality and forming process, therefore obtained using widely in electronic apparatus, automobile, mechanical means and precision instrument industry.Yet, in recent years, more and more higher requirement has been proposed for the dimensional precision of the PBT product of electronics such as the base plate of computer CD-ROM or VTR, connector, electrical component.Goods develop to thin-walled property, thin space and automation direction simultaneously, and the requirement of complex structure large-scale thin wall parts, and the moulding flowing property of PBT strongthener just becomes another major issue.It is the same with other any common glass fibre enhancing thermoplastic resins that general product level fiberglass strengthens PBT, because the importing of glass fibre has caused the flowing property variation of resin in die cavity, thereby limited its application in these areas.For this reason, people have also done a large amount of research in this respect.
From these work that present people did, the method for improving glass fibre enhancing thermoplastic resin material moulding flowability comprises the following aspects:
The first, the technology controlling and process when synthesizing by resin generates the matrix resin of high workability energy, thereby obtains moulding flowing property galss fiber reinforced resin material preferably.Geddes etc. are in U.S. Patent No. 4,997, have proposed to adopt the method for the matrix resin that a kind of high workability can be very high in 875.The glass fibre reinforcement flowing property that this method is prepared and other physical and mechanical propertiess are very desirable certainly, and other physical and mechanical propertiess of material can not be affected because of the variation of flowability yet.Yet the resin market of this special flowability is difficult for obtaining usually, is unfavorable for commercial production.Simultaneously, because every physical and mechanical properties of PBT matrix resin is subjected to mobile influence very big, therefore also inadvisable for the PBT material.
The second, free radical causes the molecular weight that the cracked method reduces matrix resin, thus the moulding flowing property of feed glass fiber-reinforced resin material.As Yang Guisheng etc. in Chinese patent No.19113507.5, adopted a kind of addition at 1% ~ 10% superoxide as radical initiator.This method obtains the glass fibre reinforcement of high workability energy with comparalive ease, but the loss of the impact property of the material that obtains is very big.
The 3rd, in glass fiber reinforcement system, add a certain amount of lubricant, this also can improve the moulding flowing property of galss fiber reinforced resin material.But used lubricant can cause other physical and mechanical propertiess of material equally usually, as the deterioration of tensile strength, impelling strength.In addition, general lubricant also can cause disadvantageous effect to the machine-shaping of material, as the fusion time of material in barrel prolonged, thereby has prolonged the cycle of whole moulding, is unfavorable for the reduction of production cost.The work of this respect comprises: Wurmb etc. are in U.S. Patent No. 4,080, a kind of method of adding 0.1%～2% low molecular weight polyethylene wax in glass fibre enhancing system that proposes in 349.This polyethylene wax the has been a kind of grafting low-molecular-weight wax of 2%～50% polar group.The glass fibre reinforcement that adopts this method to prepare has the characteristics of high workability and high tenacity, and other physical and mechanical propertiess of material are influenced less simultaneously.But he with regard to do not mention this low-molecular-weight wax to plasticizing effect in the forming materials process influenced problem.In addition, Efner is in U.S. Patent No. 5,091, also proposed to adopt the method for a kind of fatty acid ester and sodium stearate in 457.Though adopt this method can obtain the good glass fibre reinforcement of flowing property, he does not illustrate the influence of these additives for other physical and mechanical propertiess of material equally.
The 4th, the polyester material of employing special property is as the liquid crystal polyester material.The research of this respect is a lot, as Nagano in U.S. Patent No. 5,976,406 and Nitta etc. in U.S. Patent No. 5,399, all proposed to make in 656 prepare in this way high workability can glass fibre reinforcement.Because liquid crystal specific molecule structure, therefore, its processing flowability in moulding process is splendid.Adopt the prepared material of this method to be suitable for very much thin-walled or baroque electronics, electrical component, as rly., coil, junctor, diverter and clutch coupling etc.But liquid crystal material also has its disadvantageous one side, and its impelling strength is normally very poor.
Therefore, be necessary further to strengthen this research work on the one hand, develop the glass fibre that a kind of technology is easy, cheap, good, the every physical and mechanical properties of moulding flowing property is good and strengthen the PBT material.
Summary of the invention
The purpose of this invention is to provide the preparation method that a kind of preparation technology is simple, cost is low, the high workability of every physical and mechanical properties excellence energy glass fibre strengthens the PBT matrix material.
For realizing that the object of the invention provides following technical proposals: a kind of glass fibre enhanced PBT matrix material of high workability energy, comprise glass fibre, PBT, it is characterized in that, also comprise flow improver additive ethylenic unsaturation chloroflo, toughness reinforcing and compatilizer, oxidation inhibitor, each component is mixed with by following weight percentage: (%)
PBT 45-85
Flow improver additive 1-5
Toughness reinforcing, compatilizer 1.5-20
Oxidation inhibitor 0.2-1
Glass fibre 10-37
Wherein, described toughness reinforcing, compatilizer is a kind of ethylene copolymer that contains epoxy-functional, comprises the graft copolymer of ethylene-propylene rubber(EPR) and methacrylic glyceryl ester; Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, or a kind of or its mixture in three (2,4 one di-tert-butylphenol) phosphorous acid ester.The present invention adopts a kind of ethylenic unsaturation chloroflo certain polar group, that have the highly linear feature strengthens the PBT matrix material as glass fibre flow improver additive agent that has, make material in moulding process, in mold cavity, show splendid flowing property by this flow improver additive, thereby under normal forming pressure, can be used in the moulding of various thin wall parts.In addition, therefore the prolongation of fusion time when the adding of this flow improver additive can't cause forming materials can't cause the prolongation of production cycle, the rising of manufacturing cost therefrom.And the adding of this flow improver additive does not cause the reduction of other physical and mechanical propertiess of material yet, every physical and mechanical properties excellence of prepared material.
In the above-mentioned composite-material formula, described PBT is a relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.6～0.9.
In the above-mentioned composite-material formula, flow improver additive is relative density 0.98～1.0g/cm
3, 95～102 ℃ of fusing points, the ethylenic unsaturation chloroflo that adopts Fischer-Tropsch technology to synthesize, have polar group, have the highly linear feature produces as South Africa Sasol company, and trade names are Ehance.
Toughness reinforcing, compatilizer produces for Dupont company, and trade names are the ethylene copolymer that contains epoxy-functional of Elvaloy PTW; Oxidation inhibitor produces for Ciba company, and trade names are Irganox 1010, and chemical name is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester.
The preparation method that a kind of high workability energy of the present invention glass fibre strengthens the PBT matrix material is as follows:
(1) each component by weight percentage composition weigh raw material;
(2) with glass fibre through silane coupling agent;
(3) PBT that weighs in (1), flow improver additive, toughness reinforcing and compatilizer, oxidation inhibitor are done in super mixer and mixed 3-5 minutes;
(4) mixed batching in (3) is placed twin screw extruder with the glass fibre blending of handling through step (2), through melt extrude, granulation, each zone temperatures of its screw rod 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.
Described silane coupling agent is at least vinyl trichloro silane, vinyl three (β-methoxyethoxy) silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(β-amino-ethyl)-γ-TSL 8330, γ-An Bingjisanyiyangjiguiwan, N-phenyl-γ-TSL 8330, a kind of in compound of this group of γ-methyl coloured glaze base propyl trimethoxy silicane and γ-r-chloropropyl trimethoxyl silane.
Silane coupling agent is preferably γ-An Bingjisanyiyangjiguiwan.
Advantage of the present invention is:
1, the present invention has used effective flow improver additive, the moulding flowing property of obtained matrix material is greatly improved, this flow improver additive has no adverse effects to every physical and mechanical properties of material simultaneously, and the every physical and mechanical properties of prepared material is very excellent.
2, the prepared glass fibre of the present invention strengthens the PBT matrix material to have fusion time simultaneously few, the characteristics that shaping cycle is short.
3, the preparation technology of the glass fibre enhancing PBT 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, PBT is a relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate PBT of melt viscosity 0.3～1.0; Flow improver additive is relative density 0.98～1.0g/cm
3, 95～102 ℃ of fusing points, the ethylenic unsaturation chloroflo that adopts Fischer-Tropsch technology to synthesize, have polar group, have the highly linear feature produces as South Africa Sasol company, and trade names are Ehance; Toughness reinforcing, compatilizer 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 each component by weight percentage composition take by weighing, wherein, PBT is 66.3%, flow improver additive Ehancel%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again melt extrudes through 230～255 ℃, and matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Embodiment 2
With each component by weight percentage composition take by weighing, wherein, the PBT weight ratio is 65.3%, flow improver additive Ehance 2%, PTW 2.5% and 1010,0.2% in super mixer, under room temperature state, do to mix after, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 230～255 ℃ melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Embodiment 3
With each component by weight percentage composition take by weighing, wherein, the PBT weight ratio is 64.3%, flow improver additive Ehance 3%, PTW 2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again melt extrudes through 230～255 ℃, and matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Embodiment 4
With each component by weight percentage composition take by weighing, wherein, the PBT weight ratio is 63.3%, flow improver additive Ehance 4%, PTW 2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again melt extrudes through 230～255 ℃, and matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Embodiment 5
With each component by weight percentage composition take by weighing, wherein, with the PBT weight ratio be 62.3%, flow improver additive Ehance 5%, PTW 2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again melt extrudes through 230～255 ℃, and matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Comparative Examples 1
With each component by weight percentage composition take by weighing, wherein, the PBT weight ratio is 67.3%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again melt extrudes through 230～255 ℃, and matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Comparative Examples 2
With each component by weight percentage composition take by weighing, wherein, the PBT weight ratio is 64.3%, oxidized polyethlene wax 3%, PTW 2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again melt extrudes through 230～255 ℃, and matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 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.
Comparative Examples 3
With the PBT weight ratio be 64.3%, superoxide two 2,5 initiators 3%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state 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 230～255 ℃, matrix material is made in granulation.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, PTW2.5%, 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.
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 ISO527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO178, 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 ISO179, and specimen size is 55*6*4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO75, and specimen size is 127*12.7*3.2mm, and load is 1.82MPa; Melt flow index (MFR) is undertaken by ISO1183, and test condition is 250 ℃, 3.8Kg.
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 moulding flowing property judgment method 1 of material is undertaken by measured melting index numerical value, and the big more flowing property that shows of numerical value is good more; The moulding flowing property judgment method 2 of material represents that by the minimum injection pressure that is full of the 127*12.7*3.2mm sample the more for a short time flowing property that shows of numerical value is good more.The fusion time of material can reach the shortest storing time representation that the specimen surface material is evenly distributed by 150*100*3.22mm sample moulding under the same conditions, and the time, short more expression fusion cycle was short more.
The prescription of embodiment 1-5 and Comparative Examples 1-5 and every The performance test results be each table as follows:
Table 1 Example formulations and material property table
| The matrix material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| PBT(％) | 66.3 | 65.3 | 64.3 | 63.3 | 62.3 |
| Flow improver additive Ehance | 1 | 2 | 3 | 4 | 5 |
| PTW(％) | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| 1010(％) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Glass fibre (%) | 30 | 30 | 30 | 30 | 30 |
| Heat-drawn wire (1.82MPa) (℃) | 211 | 210 | 209 | 209 | 204 |
| Unnotched impact strength (kJ/m 2) | 43 | 42 | 42 | 41 | 35 |
| Tensile strength (MPa) | 118 | 116 | 115 | 115 | 105 |
| Elongation at break (%) | 2.5 | 2.6 | 2.8 | 2.9 | 2.5 |
| Flexural strength (MPa) | 186 | 185 | 184 | 185 | 174 |
| Modulus in flexure (MPa) | 8500 | 8400 | 8360 | 8300 | 8100 |
| Melt-flow refers to (MFR) (g/10min) | 5.0 | 9.0 | 15.0 | 18.0 | 22 |
| Minimum injection pressure (MPa) | 70 | 65 | 55 | 50 | 45 |
| Fusion time (S) | 5 | 5 | 5 | 5 | 5 |
Table 2 Comparative Examples prescription and material property table
Table 1 data show, use flow improver additive Ehance can greatly improve the moulding flowing property of material in the matrix material of glass fibre enhancing PBT.The addition of flow improver additive Ehance to material forming materials flowing property influence very big.When addition during in 3 ~ 4% such scopes, the moulding flowability problem of material solves ideally, and other every performances of material are unaffected substantially simultaneously.When addition surpassed this scope, though the moulding flowing property of material is improved further, other physical and mechanical propertiess, particularly impact property of material but be subjected to bigger destruction.In addition, it can also be seen that therefore the adding of this flow improver additive can obtain to have the high workability material of practical value to other every physical and mechanical properties influences and little of material from table 1.
We are as can be seen in the middle of the comparison of table 1 embodiment and table 2 Comparative Examples: do not add the material of any flow improver additive, its physical and mechanical properties is very high, but its moulding flowing property is not very desirable.Added the material that oxidized polyethlene wax is done flow improver additive, its moulding flowing property has also obtained suitable improvement, and the every physical and mechanical properties of other of material is also preferable, but because the adding of oxidized polyethlene wax makes the fusion time of material when moulding prolong greatly, from the angle of producing, this is very disadvantageous.Added initiator two 2,5 material, its moulding flowing property has also obtained suitable improvement, and the fusion time during forming materials is also uninfluenced, but then, because it is very big that the adding of oxidized polyethlene wax makes that but the physical and mechanical properties, particularly impact property of material descend, this also is disadvantageous for material.
Claims (6)
- A high workability can glass fibre enhanced PBT matrix material, comprise glass fibre, PBT, it is characterized in that also comprise flow improver additive ethylenic unsaturation chloroflo, toughness reinforcing and compatilizer, oxidation inhibitor, each component is mixed with by following weight percentage %:PBT 45-85Flow improver additive 1-5Toughness reinforcing, compatilizer 1.5-20Oxidation inhibitor 0.2-1Glass fibre 10-37Wherein, described toughness reinforcing and compatilizer is a kind of ethylene copolymer that contains epoxy-functional, comprises the graft copolymer of ethylene-propylene rubber(EPR) and methacrylic glyceryl ester; Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, or a kind of or its mixture in three (2,4 one di-tert-butylphenol) phosphorous acid ester; Described flow improver additive is relative density 0.98～1.0g/cm 3, 95～102 ℃ of fusing points, the ethylenic unsaturation chloroflo that has polar group, has the highly linear feature.
- 2. the glass fibre enhanced PBT matrix material of a kind of high workability energy according to claim 1 is characterized in that described PBT is a relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.6～0.9.
- 3. the glass fibre enhanced PBT matrix material of a kind of high workability energy according to claim 1 is characterized in that described glass fiber diameter is the 6-17 micron.
- 4. the preparation method of the glass fibre enhanced PBT matrix material of high workability energy according to claim 1 is characterized in that its method is as follows:(1) each component by weight percentage composition weigh raw material;(2) with glass fibre through the silane coupling agent coupling;(3) PBT that weighs in (1), flow improver additive, toughness reinforcing and compatilizer, oxidation inhibitor are done in super mixer and mixed 3-5 minutes;(4) mixed batching in (3) is placed twin screw extruder with the glass fibre blending of handling through step (2), through melt extrude, granulation, each zone temperatures of its screw rod 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.
- 5. the preparation method of the glass fibre enhanced PBT matrix material of high workability energy according to claim 4, it is characterized in that, described silane coupling agent is at least vinyl trichloro silane, vinyl three (β-methoxyethoxy) silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(β-amino-ethyl)-γ-TSL 8330, γ-An Bingjisanyiyangjiguiwan, N-phenyl-γ-TSL 8330, a kind of in γ-methyl coloured glaze base propyl trimethoxy silicane and the γ-r-chloropropyl trimethoxyl silane.
- 6. the preparation method of the glass fibre enhanced PBT matrix material of high workability energy according to claim 5 is characterized in that described silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.
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| CN101012331B (en) * | 2007-01-26 | 2010-06-02 | 南京聚隆科技股份有限公司 | High flowability modified PBT composite material and preparing method thereof |
| CN101851401A (en) * | 2010-03-09 | 2010-10-06 | 上海锦湖日丽塑料有限公司 | High-fluidity polyester composition and preparation method |
| CN111234475A (en) * | 2020-01-17 | 2020-06-05 | 中广核俊尔（上海）新材料有限公司 | High-fluidity reinforced PBT material and preparation method thereof |
| CN112679918B (en) * | 2020-12-14 | 2023-04-18 | 江苏金发科技新材料有限公司 | Laser-weldable PBT composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4080349A (en) * | 1973-09-28 | 1978-03-21 | Basf Aktiengesellschaft | Glass-fiber-reinforced thermoplastic molding compositions showing improved flowability and toughness |
| US4687795A (en) * | 1984-12-24 | 1987-08-18 | Allied Corporation | Polyester molding compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4080349A (en) * | 1973-09-28 | 1978-03-21 | Basf Aktiengesellschaft | Glass-fiber-reinforced thermoplastic molding compositions showing improved flowability and toughness |
| US4687795A (en) * | 1984-12-24 | 1987-08-18 | Allied Corporation | Polyester molding compositions |
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