CN1563186A - Low warped and high surfaceness PBT composite material enhanced by fiberglass - Google Patents
Low warped and high surfaceness PBT composite material enhanced by fiberglass Download PDFInfo
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- CN1563186A CN1563186A CN 200410017803 CN200410017803A CN1563186A CN 1563186 A CN1563186 A CN 1563186A CN 200410017803 CN200410017803 CN 200410017803 CN 200410017803 A CN200410017803 A CN 200410017803A CN 1563186 A CN1563186 A CN 1563186A
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- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000011152 fibreglass Substances 0.000 title description 2
- 239000003365 glass fiber Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 5
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 50
- 239000011159 matrix material Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 159000000003 magnesium salts Chemical class 0.000 claims description 17
- -1 pentaerythritol ester Chemical class 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229920000728 polyester 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
- 239000002994 raw material Substances 0.000 claims description 4
- 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 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 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
- 150000001875 compounds Chemical class 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
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 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
- 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
- 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 1
- 239000000463 material Substances 0.000 abstract description 37
- 150000002148 esters Chemical class 0.000 abstract 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 238000005453 pelletization Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000002708 enhancing effect Effects 0.000 description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920003314 Elvaloy® Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011236 particulate material Substances 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
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100024482 Cell division cycle-associated protein 4 Human genes 0.000 description 1
- 241001251094 Formica Species 0.000 description 1
- 101000980898 Homo sapiens Cell division cycle-associated protein 4 Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 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 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
A glass fibre reinforced PBT composite is made of PBT, magnesia salt whisker, flexibilizing compatilizer, antioxygen and glass fibre as flexibilizing compatilizer is ethylene copolymer containing grafted copolymer of ethylene-propylene rubber and methylpropylene glyceride, antioxygen is one of terapentaerythritol ester or triphosphorous acid ester. Its preparing process includes mixing base body of PBT with modifier, flexibilizing compatibilizer and antioxygen, feeding the mixed material together with glass fibre into extruder for melting, extruding and then pelletizing.
Description
Technical field
Glass fiber reinforced polyester butylene terephthalate (the calling PBT in the following text) matrix material of a kind of low warpage of the present invention, high surface gloss relates to the preparation method of a kind of polymer composite engineering material and this matrix material, more specifically relates to a kind of glass fibre that improves the goods angularity that can show and strengthens the PBT matrix material.
Background technology
Owing to adopt the component of 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, because the increase in demand of large-scale thin wall parts, the low warpage of PBT material becomes a major issue.And generally the buckling deformation of product level fiberglass enhancing PBT is big, and warpage issues once made the market sale of PBT sink into awkward situation, so each production firm pays much attention to the research and development of being devoted to low warpage grade PBT.
PBT product warpage issues can be improved by adopting low injection speed, long cooling time in theory, yet shaping cycle prolongs thus, thereby has caused the cost increase.
Another method that solves PBT product warpage issues is to adopt mineral-filled, mineral and the composite filled enhancing modified of glass.People did a lot of work in this respect.
Vollenberg etc. are in U.S. Patent No. 5,840, have proposed to adopt a kind of method of glass of special cross-section shape in 798, thereby by this glass and common glass together are added on the purpose that reaches the control warpage in the PBT resin.Efner is in U.S. Patent No. 5,091, proposed in 457 to adopt a kind of method of specific glass scale also can improve the problem of this material product warpage.But these two kinds of methods all need to use a kind of special glass filler, are unfavorable for the commercial production of practicability in enormous quantities undoubtedly.
Kochanowski etc. are in U.S. Patent No. 4,460,731, Phipps is in U.S. Patent No. 4,140, and 669, Kokai is at Japanese Patent No.60-124649 and Kohyo has proposed the use talcum powder in Japanese Patent No.1-502833 and glass mixes the enhanced method of filling.Goedde etc. are in U.S. Patent No. 4,203, have introduced a kind of method of using the potter's clay of needle-like Calucium Silicate powder, silane treatment in 887.Yet, though these methods can make the intensity of material and toughness be subjected to infringement simultaneously so that the warpage of PBT material product is improved also.
Asai etc. are in U.S. Patent No. 5,428, and the graphite that has proposed employing particle diameter 〉=5 μ in 100 mixes with the talcum powder of particle diameter 〉=5 μ the warpage issues of material is carried out improved method.But he does not mention the influence of these additives to other physical and mechanical properties of material.
Wilder etc. are in U.S. Patent No. 5,075, have adopted a kind of glass microballon and common glass through special processing to mix to improve the method for warpage in 354.But he does not mention the influence problem of this additive to other physical and mechanical properties of material equally.
Cohen is in U.S. Patent No. 4,140, proposed to adopt in 67 and added a certain amount of polyphenylene sulfide to improve the method for warpage.Liu is in U.S. Patent No. 5,026, adopted the method for a kind of high-molecular weight polyester elastomer as material warp properties-correcting agent in 760.But these two kinds of material price costlinesses, thereby also caused the rising of PBT material cost.
Hepp is in U.S. Patent No. 4,393, in 153 and Keep in U.S. Patent No. 4,874, all proposed to add simultaneously the method for mica and rubber in 809 so that material is under the prerequisite that warpage issues is solved, toughness is guaranteed.But it remains to sacrifice certain intensity and exchanges the toughness that improves material for.
Therefore, how to obtain can reach overall equilbrium between the intensity, toughness of a kind of warpage properties of product and material, the relatively reasonable again method of cost still is worth people to make great efforts to explore simultaneously.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation technology is simple, cost is low, the low warpage of every physical and mechanical properties excellence, high surface finish glass fibre strengthen PBT matrix material and preparation method thereof.
The object of the invention can be achieved through the following technical solutions: a kind of low warpage, high surface finish glass fibre strengthen the PBT matrix material, comprise glass fibre, PBT, characteristics are also to comprise warpage properties-correcting agent magnesium salt whisker, toughness reinforcing and compatible agent, oxidation inhibitor, and each component is made by following weight percentage: (%)
PBT??????????????????????????????????????45-80
Magnesium salt whisker 5-25
Toughness reinforcing, compatible agent 1.5-20
Oxidation inhibitor 0.2-1
Glass fibre 10-37 wherein, described toughness reinforcing, compatible agent 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 in three (2, the 4-di-tert-butylphenol) phosphorous acid ester.
In the above-mentioned composite-material formula, the PBT of indication 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, magnesium salt whisker is relative density 2.2～2.4g/cm
3, diameter＜1.0 micron, the single crystal fibre shape white powder that mean length is 10～80 microns, its chemical formula is MgSO
45Mg (OH)
2.3H
2O.The present invention has adopted a kind of warpage properties-correcting agent with single crystal fibre shape white mineral powder of certain length-to-diameter ratio as glass fibre enhancing PBT matrix material, makes that by this properties-correcting agent the warpage issues of material product is solved well.In addition, because this properties-correcting agent itself has certain length-to-diameter ratio, so it has certain enhancing ability to material simultaneously, thereby all other physical and mechanical propertiess of prepared material are very excellent.
Toughness reinforcing, compatible agent can select for use Dupont company to produce, and trade names are the ethylene copolymer that contains epoxy-functional of Elvaloy PTW.
In the above-mentioned composite-material formula, described glass fiber diameter is the 6-17 micron.In order to improve glass fibre and PBT compatibility, glass fibre is handled through silane coupling agent, described silane coupling agent is at least vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, a kind of material in this group compound of γ-methyl coloured glaze base propyl trimethoxy silicane and γ-r-chloropropyl trimethoxyl silane.
Wherein, selected silane coupling agent is preferably γ-An Bingjisanyiyangjiguiwan.
The preparation method that a kind of low warpage of the present invention, high surface finish glass fibre strengthen the PBT matrix material is as follows:
(1) weighs raw material by above-mentioned prescription each component weight percentage preparation;
(2) glass fibre is handled through silane coupling agent;
(3) polyester, magnesium salt whisker, toughness reinforcing and compatible agent, the oxidation inhibitor that weigh in (1) are done in super mixer and mixed 3-5 minute;
(4) raw materials mixed is placed twin screw extruder with the glass fibre blending of (2) gained, through melt extrude, 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.
Utilize aforesaid method, prepared material surface glossiness is very good.
Advantage of the present invention is:
1, the present invention has used warpage properties-correcting agent efficiently, and the angularity of obtained matrix material is able to desirable the solution, and this properties-correcting agent has certain reinforced effects to material simultaneously, and therefore all other physical and mechanical propertiess of prepared material are also very excellent.
2, the prepared glass fibre enhancing of the present invention PBT matrix material has the characteristics of high surface gloss simultaneously.
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 relative density 1.31-1.35, fusing point 220-230 ℃, and the polybutylene terephthalate PBT of melt viscosity 0.3-1.0; Magnesium salt whisker is relative density 2.2-2.4g/cm
3, diameter＜1.0 micron, the single crystal fibre shape white powder of mean length 10-80 micron, its chemical formula is MgSO
45Mg (OH)
2.3H
2O; Toughness reinforcing, compatible agent 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 each component weight percent be: PBT 59.3%, magnesium salt whisker 8%, 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, 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 weight percent PBT weight ratio be 53.3%, magnesium salt whisker 14%, 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, 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 the PBT weight ratio be 49.3%, magnesium salt whisker 18%, 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, 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 weight percent PBT weight ratio be 45.3%, magnesium salt whisker 22%, 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 mouthfuls, 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 the PBT weight ratio be 67.3%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, and glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, melt extrude through 230～255 mouthfuls, 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 the PBT weight ratio be 49.3%, talcum powder 18%, 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 mouthfuls, 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 49.3%, mica 18%, 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, 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 4
With the PBT weight ratio be 49.3%, glass microballon 18%, 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 mouthfuls, 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.
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; The surface smoothness of material product is undertaken by self-defining method, and specimen size is 150*100*3.22mm; The angularity of material product is undertaken by self-defining method, and specimen size is φ 80*2mm.
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 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 angularity of material characterizes according to the highest point of above-mentioned disk generation warpage after strain radian curve and the vertical range (mm) of lowest part.
The prescription of embodiment 1-4 and Comparative Examples 1-4 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 |
| ??PBT(％) | ???59.3 | ???53.3 | ???49.3 | ???45.3 |
| Magnesium salt whisker | ???8 | ???14 | ???18 | ???22 |
| ??PTW(％) | ???2.5 | ???2.5 | ???2.5 | ???2.5 |
| ??1010(％) | ???0.2 | ???0.2 | ???0.2 | ???0.2 |
| Glass fibre (%) | ???30 | ???30 | ???30 | ???30 |
| Heat-drawn wire (1.82MPa) (℃) | ???210 | ???210 | ???210 | ???210 |
| Unnotched impact strength (kJ/m 2) | ???42 | ???38 | ???38 | ???32 |
| Tensile strength (MPa) | ???115 | ???113 | ???112 | ???105 |
| Elongation at break (%) | ???2.5 | ???2.5 | ???2.2 | ???2.0 |
| Flexural strength (MPa) | ???180 | ???177 | ???175 | ???168 |
| Modulus in flexure (MPa) | ???9500 | ???11000 | ???12500 | ???13000 |
| Apparent mass | Smooth, glossy | Smooth, glossy | Smooth, glossy | Smooth, glossy |
| Angularity (mm) | ???1.5 | ???0.5 | ???0.1 | ???0.1 |
Table 2 Comparative Examples prescription and material property table
| The matrix material title | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 2 |
| ?PBT(％) | ?67.3 | ?49.3 | ?49.3 | ?49.3 |
| Lime carbonate (%) | ?- | ?18 | ?- | ?- |
| Mica (%) | ?- | ?- | ?18 | ?- |
| Glass microballon (%) | ?- | ?- | ?- | ?18 |
| ?PTW(％) | ?2.5 | ?2.5 | ?2.5 | ?2.5 |
| ?1010(％) | ?0.2 | ?0.2 | ?0.2 | ?0.2 |
| Glass fibre (%) | ?30 | ?30 | ?30 | ?30 |
| Heat-drawn wire (1.82MPa) (℃) | ?212 | ?195 | ?202 | ?203 |
| Unnotched impact strength (kJ/m 2) | ?45 | ?25 | ?30 | ?27 |
| Tensile strength (MPa) | ?118 | ?101 | ?105 | ?103 |
| Elongation at break (%) | ?2.5 | ?2.0 | ?2.0 | ?2.0 |
| Flexural strength (MPa) | ?188 | ?162 | ?168 | ?166 |
| Modulus in flexure (MPa) | ?8100 | ?9500 | ?10800 | ?10000 |
| Apparent mass | Glass emergence on the surface is serious | A large amount of cloudings | A large amount of cloudings | A large amount of cloudings |
| Angularity | ?2.5 | ?1.5 | ?0.8 | ?0.7 |
Table 1 data show, use magnesium salt whisker can play the effect of fine improvement to the warpage issues of product in the matrix material of glass fibre enhancing PBT.The addition of magnesium salt whisker is very big to the influence of material warp degree and other physical and mechanical properties.When addition during in 14～18% such scopes, it is ideal that the warpage issues of material solves, and all other performances of material are influenced also less simultaneously.When addition surpassed this scope, though the warpage of material has been able to solution, other physical and mechanical properties, particularly impact property of material but be subjected to bigger destruction.In addition, we find to adopt the material of this method preparation simultaneously, and the characteristic of best bright finish has all appearred in its product surface.
We are as can be seen in the middle of the comparison of table 1 embodiment and table 2 Comparative Examples: do not add any filler and make the glass fibre that warpage improves and strengthen the PBT material, its physical and mechanical properties is very high, but its angularity also is maximum, and simultaneously with the glass emergence on the surface phenomenon.Three groups of materials that add talcum powder, mica and glass microballon have been distinguished, the warping phenomenon of its product has all obtained improvement in various degree, but all not having the magnesium salt whisker effect of adding same components is showing, and its physical and mechanical properties of one side, particularly impact being subjected to considerable influence, the phenomenon of a large amount of cloudings has all appearred in the surface of its product on the other hand.
Claims (7)
1. a low warpage, high surface finish glass fibre strengthen the PBT matrix material, comprise glass fibre, PBT, it is characterized in that also comprising warpage properties-correcting agent magnesium salt whisker, toughness reinforcing and compatible agent, oxidation inhibitor, each component is made by following weight percentage: (%)
PBT?????????????????????????????????45-80
Magnesium salt whisker 5-25
Toughness reinforcing, compatible agent 1.5-20
Oxidation inhibitor 0.2-1
Glass fibre 10-37
Wherein, described toughness reinforcing, compatible agent 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 in three (2,4 one di-tert-butylphenol) phosphorous acid ester.
2. a kind of low warpage according to claim 1, high surface finish glass fibre strengthen the PBT matrix material, it 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. a kind of low warpage according to claim 1, high surface finish glass fibre strengthen the PBT matrix material, it is characterized in that described magnesium salt whisker is relative density 2.2～2.4g/cm
3, diameter＜1.0 micron, the single crystal fibre shape white powder that mean length is 10～80 microns, its chemical formula is MgSO
45Mg (OH)
2.3H
2O.
4. a kind of low warpage according to claim 1, high surface finish glass fibre strengthen the PBT matrix material, it is characterized in that described glass fiber diameter is the 6-17 micron.
5. a kind of low warpage according to claim 1, high surface finish glass fibre strengthen the preparation method of PBT matrix material, it is characterized in that its method is as follows:
(1) weighs raw material by the preparation of each component weight percentage;
(2) glass fibre is handled through silane coupling agent;
(3) polyester, magnesium salt whisker, toughness reinforcing and compatible agent, the oxidation inhibitor that weigh in (1) 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 of (2) gained, 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.
6. a kind of low warpage according to claim 5, the high surface finish glass fibre strengthens the preparation method of PBT matrix material, it is characterized in that, described silane coupling agent is at least vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, a kind of in compound of this group of γ-methyl coloured glaze base propyl trimethoxy silicane and γ-r-chloropropyl trimethoxyl silane.
7. a kind of low warpage according to claim 6, high surface finish glass fibre strengthen the preparation method of PBT matrix material, it is characterized in that described silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.
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| CN 200410017803 CN1563186B (en) | 2004-04-15 | 2004-04-15 | Low warped and high surfaceness PBT composite material enhanced by fiberglass |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102464868A (en) * | 2010-11-05 | 2012-05-23 | 合肥杰事杰新材料股份有限公司 | Scratch-resistant polybutylene terephthalate composition and preparation method thereof |
| CN102040806B (en) * | 2009-10-19 | 2012-09-05 | 浙江三威防静电装备有限公司 | High temperature resistance anti-static low warpage PBT / PET alloy composite material and its manufacturing method |
| CN106084614A (en) * | 2016-06-20 | 2016-11-09 | 吕智 | Prevent the preparation method of the compatilizer of PBT alloy material warp and prepared compatilizer thereof |
| CN106280320A (en) * | 2016-08-31 | 2017-01-04 | 广东顺德顺炎新材料股份有限公司 | A kind of low warpage highlight antiflaming polybutylene terephthalate (PBT) and preparation method thereof |
| CN106380800A (en) * | 2016-10-08 | 2017-02-08 | 上海加略实业有限公司 | High heat-resistant spraying-free glass fiber reinforced PBT/PET alloy and preparation method thereof |
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| CN110128799A (en) * | 2019-05-31 | 2019-08-16 | 珠海格力新材料有限公司 | PBT composite material and preparation method thereof |
| CN112239587A (en) * | 2019-07-19 | 2021-01-19 | 沈阳科通塑胶有限公司 | Low-warpage glass fiber reinforced polybutylene terephthalate material and preparation method thereof |
| CN112852131A (en) * | 2021-02-02 | 2021-05-28 | 苏州塑发生物材料有限公司 | High-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102040806B (en) * | 2009-10-19 | 2012-09-05 | 浙江三威防静电装备有限公司 | High temperature resistance anti-static low warpage PBT / PET alloy composite material and its manufacturing method |
| CN102464868A (en) * | 2010-11-05 | 2012-05-23 | 合肥杰事杰新材料股份有限公司 | Scratch-resistant polybutylene terephthalate composition and preparation method thereof |
| CN106084614A (en) * | 2016-06-20 | 2016-11-09 | 吕智 | Prevent the preparation method of the compatilizer of PBT alloy material warp and prepared compatilizer thereof |
| CN106280320A (en) * | 2016-08-31 | 2017-01-04 | 广东顺德顺炎新材料股份有限公司 | A kind of low warpage highlight antiflaming polybutylene terephthalate (PBT) and preparation method thereof |
| CN106380800A (en) * | 2016-10-08 | 2017-02-08 | 上海加略实业有限公司 | High heat-resistant spraying-free glass fiber reinforced PBT/PET alloy and preparation method thereof |
| CN109081894A (en) * | 2018-07-20 | 2018-12-25 | 厦门科艾斯塑胶科技有限公司 | A kind of high fluidity toughener and preparation method thereof |
| CN109081894B (en) * | 2018-07-20 | 2020-12-15 | 厦门科艾斯塑胶科技有限公司 | High-fluidity toughening agent and preparation method thereof |
| CN110128799A (en) * | 2019-05-31 | 2019-08-16 | 珠海格力新材料有限公司 | PBT composite material and preparation method thereof |
| CN112239587A (en) * | 2019-07-19 | 2021-01-19 | 沈阳科通塑胶有限公司 | Low-warpage glass fiber reinforced polybutylene terephthalate material and preparation method thereof |
| CN112852131A (en) * | 2021-02-02 | 2021-05-28 | 苏州塑发生物材料有限公司 | High-surface-quality low-density magnesium salt whisker reinforced polylactic acid composite material and preparation method thereof |
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