CN100448929C - Anti color distortion PDT material enhanced by halogeton flame retardant fiberglass - Google Patents
Anti color distortion PDT material enhanced by halogeton flame retardant fiberglass Download PDFInfo
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- CN100448929C CN100448929C CNB2004100178072A CN200410017807A CN100448929C CN 100448929 C CN100448929 C CN 100448929C CN B2004100178072 A CNB2004100178072 A CN B2004100178072A CN 200410017807 A CN200410017807 A CN 200410017807A CN 100448929 C CN100448929 C CN 100448929C
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- Prior art keywords
- thermal oxidation
- polybutylene terephthalate
- oxidation stabilizer
- matrix material
- glass fiber
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- 239000000463 material Substances 0.000 title abstract description 39
- 239000003063 flame retardant Substances 0.000 title abstract description 12
- 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 title abstract description 9
- 241000786137 Halogeton glomeratus Species 0.000 title 1
- 239000011152 fibreglass Substances 0.000 title 1
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 63
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003365 glass fiber Substances 0.000 claims abstract description 53
- 239000003381 stabilizer Substances 0.000 claims abstract description 52
- 230000003647 oxidation Effects 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- -1 flame-retardant halogen Chemical class 0.000 claims abstract description 34
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims description 32
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 27
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000005050 vinyl trichlorosilane Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000012745 toughening agent Substances 0.000 abstract 2
- 239000000779 smoke Substances 0.000 abstract 1
- 239000007822 coupling agent Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002708 enhancing effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- NFCPRRWCTNLGSN-UHFFFAOYSA-N 2-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NC1=CC=CC=C1 NFCPRRWCTNLGSN-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920003314 Elvaloy® Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to flame-retardant halogen glass fibre reinforced polybutylene terephthalate (PBT) material with color distortion resistance, particularly to polymer composite material and a preparation method thereof. Low-smoke flame-retardant glass fibre reinforced PBT composite material is composed of 45% to 75% of PBT, 8% to 15% of decabromo phenylate, 3% to 5% of antimonous oxide, 0.2% to 1% of polytetrafluorethylene, 1.5% to 20% of toughening agents and compatilizers, 0.1% to 0.5% of thermal oxidation stabilizer 245, 0.1% to 0.5% of thermal oxidation stabilizer 618, 0.1% to 0.5% of thermal oxidation stabilizer DSTP and 10% to 37% of glass fibers. The preparation method is characterized in that the PBT is used as a basal body, the decabromo phenylate, the antimonous oxide, the polytetrafluorethylene, the toughening agent, the compatilizer, the thermal oxidation stabilizer 245, the thermal oxidation stabilizer 618 and the thermal oxidation stabilizer DSTP are added and mixed with the basal body, and then a mixture and the glass fibers are melted, extruded and granulated through a double-screw extruder. The present invention has the advantages of simple preparation process and low cost; material has the advantages of no color distortion and excellent mechanical properties.
Description
Technical field
A kind of anti-look of the present invention becomes has halogen combustion-proof glass fiber enhancing polybutylene terephthalate (calling PBT in the following text) material to relate to a kind of polymer composite and preparation method thereof, more specifically relates to a kind of anti-look that contains efficient heat stabilizing system and becomes, has the halogen combustion-proof glass fiber to strengthen the PBT material.
Background technology
Glass fibre strengthens the PBT material and not only has excellent physical and mechanical properties, as physical strength height, resistance to fatigue and dimensional stability are good, creep is little, ageing-resistant performance is excellent, and its electric property is also very excellent, as its volume specific resistance and dielectric strength height, arc resistance can be good, under moist hot environment electric performance stablity, so be the ideal material of making electronics, electric parts.And general electronics, electric parts all have fire-retardant requirement in various degree.Therefore, the fire-retardant problem that the glass fibre that uses in electronics, electric field strengthens the PBT material is a major issue.Usually the flame-retardant system that is used as glass fibre enhancing PBT material at present still is the bromo-antimony combined system of bromide and stibnide.In the middle of this system, because decabromodiphenyl oxide so is extensively used by domestic manufacturer with the antimonous oxide system is cheap, flame retardant effect is remarkable.Yet, practice finds, when this system melt extrudes under with thermoplastic polyester pyritous environment, because some are still for know former thereby cause the severely degrade of polyester, thereby make the physical and mechanical properties of material worsen on the one hand, also caused the serious discoloration of material on the other hand.Issue to add lustre at the pyritous processing conditions with regard to thermoplastic resin material and become with regard to this problem, under the situation that lacks effective thermo-stabilizer, all there is this problem to some extent in quite a few resin material.For this reason, people tie up to this at different thermoplastic resin bodies and do a lot on the one hand.
Van Brederode is in U.S. Patent No. 4,066, proposed a kind of stabiliser system of three components in 608 at the acrylic resin of enhancing or non-enhancing grafted propylene acid type, they are respectively thio-2 acid octadecyl ester (DSTP), distearyl pentaerythritol diphosphite (618) and 1,3,5-three (3,5 di-t-butyls-4 hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) triketone (3114).Bost etc. are in U.S. Patent No. 4,140, have also proposed the stablizer of a kind of P contained compound as expansion type flame retardant flame-retardant foam urethane in 856.
In U.S. Patent No. 3,637, proposed in 573 with a kind of phenylenediamine or similar compound method as polyurethane foam stabilizer.
In U.S. Patent No. 3,798, proposed in 184 with the reaction product of a kind of acetone and pentanoic method as polyurethane foam stabilizer.
Reale etc. are in U.S. Patent No. 4,130, have proposed the stabiliser system of resistance combustion polyurethane foam material in 513, and it is made up of the mixture between the reaction product phenyl phenylenediamine of acetone and pentanoic.
Moberly is in U.S. Patent No. 4,328, proposed a kind of stablizer that is applicable to expansion type flame retardant in 132, and this stablizer has comprised a kind of in metal phosphate, metal phosphinates, metal sulfate or the metal sulphite at least.
Yet,, be applicable to that particularly the efficient stable agent system of decabromodiphenyl oxide and antimonous oxide system combustion-proof glass fiber enhancing PBT material is not still seen special discussion as yet about being applicable to the bromo-antimony combined system of bromide and stibnide.For this reason, be necessary to develop a kind of efficiently, be applicable to the bromo-antimony combined system of bromide and stibnide, be applicable to that particularly decabromodiphenyl oxide and antimonous oxide system combustion-proof glass fiber strengthen the stabiliser system of PBT material, strengthen the PBT material thereby obtain colourless change, high performance decabromodiphenyl oxide and antimonous oxide system combustion-proof glass fiber.
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 anti-look of every physical and mechanical properties excellence becomes, has halogen combustion-proof glass fiber enhancing PBT matrix material.
For realizing above purpose, technical scheme of the present invention provides a kind of anti-look and becomes, has the halogen combustion-proof glass fiber to strengthen the PBT matrix material, comprise glass fibre, PBT, and mixed type thermo-stabilizer, decabromodiphenyl oxide, antimonous oxide, tetrafluoroethylene, toughness reinforcing and compatilizer in described PBT matrix material, have been added, described mixed type thermo-stabilizer comprises thermal oxidation stabilizer 245, thermal oxidation stabilizer 618, thermal oxidation stabilizer DSTP, and each component is mixed with by following weight percentage proportion raw material: (%)
PBT 45-75
Decabromodiphenyl oxide 8-15
Antimonous oxide 3-5
Tetrafluoroethylene 0.2-1
Toughness reinforcing and compatilizer 1.5-20
Thermal oxidation stabilizer 245 0.1-2
Thermal oxidation stabilizer 618 0.1-2
Thermal oxidation stabilizer DSTP 0.1-2
Glass fibre 10-37
Wherein, described toughness reinforcing, compatilizer 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.The present invention adopts a kind of thermal oxidation stabilizer 245, thermal oxidation stabilizer 618 and thermal oxidation stabilizer DSTP mixture as there being the halogen combustion-proof glass fiber to strengthen PBT matrix material effective stabilizer system, make material not degrade in the course of processing by this stabiliser system, look does not become.Because this stabiliser system has successfully been restrained the PBT resin in the degraded that has under halogen, the high temperature process environment, therefore prepared material can keep the not characteristic of look change, other physical and mechanical properties excellences of material simultaneously.
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.
Described decabromodiphenyl oxide is melt temperature 290-310 ℃, heat decomposition temperature＞310 ℃, bromine content＞82%, the white powder of particle diameter 5-10 micron.
In the above-mentioned composite-material formula, described antimonous oxide is melt temperature 650-660 ℃, decomposition temperature 1450-1460 ℃, and particle diameter 1500 purpose white powders.
Described tetrafluoroethylene is a particle diameter 5-10 micron, apparent density 250-300g/l, fusing point 320-330 ℃.
Described glass fiber diameter is the 6-17 micron, for improving and the PBT consistency, and can be through coupling agent treatment.
A kind of anti-look becomes, has the preparation method of halogen combustion-proof glass fiber enhancing PBT matrix material as follows:
(1) each component by weight percentage composition weigh raw material;
(2) glass fibre is handled through silane coupling agent;
(3) with PBT, decabromodiphenyl oxide, antimonous oxide, tetrafluoroethylene, toughness reinforcing and compatilizer, thermal oxidation stabilizer 245, thermal oxidation stabilizer 618 and thermal oxidation stabilizer DSTP dried mixing 3-5 minute in super mixer;
(4) raw materials mixed is placed dual-screw-stem machine with the glass fibre blending, 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.
Advantage of the present invention is:
1, the present invention has used the effective stabilizer system, and the colourless realization of obtained matrix material resembles generation.
2, the present invention is prepared has the halogen combustion-proof glass fiber to strengthen every physical and mechanical properties that the PBT matrix material has excellence 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, decabromodiphenyl oxide is melt temperature 290-310 ℃, heat decomposition temperature＞310 ℃, bromine content＞82%, the white powder of particle diameter 5-10 micron; Antimonous oxide is melt temperature 650-660 ℃, decomposition temperature 1450-1460 ℃, and particle diameter 1500 purpose white powders; Tetrafluoroethylene is a particle diameter 5-10 micron, apparent density 250-300g/l, fusing point 320-330 ℃; Toughness reinforcing, compatilizer produces for Dupont company, and trade names are the ethylene copolymer that contains epoxy-functional 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 is that Yaohua Glass-making Plant, Shanghai produces, and chemical name is a γ-An Bingjisanyiyangjiguiwan; Thermal oxidation stabilizer 245 is that Ciba company produces, and trade names are Irganox 245, chemical name be triglycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide; Thermal oxidation stabilizer 618 produces for GE company, and trade names are Weston 618, and chemical name is a distearyl pentaerythritol diphosphite; Thermal oxidation stabilizer DSTP is that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester; PBT is a relative density 1.31 ~ 1.35,220 ~ 230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.6 ~ 0.9.
Embodiment 1
With the PBT weight ratio be 53.2%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245 be 0.1%, 618 be 0.1% and DSTP0.1% in super mixer, under room temperature state, do and mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 2
With the PBT weight ratio be 53.1%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245 be 0.1%, 618 be 0.2% and DSTP0.1% in super mixer, under room temperature state, do and mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 the PBT weight ratio be 53.0%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245 be 0.1%, 618 be 0.3% and DSTP0.1% in super mixer, under room temperature state, do and mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 4
With the PBT weight ratio be 52.9%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245,0.1%, 618,0.3% and DSTP0.2% in super mixer, under room temperature state, do to mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 5
With the PBT weight ratio be 52.8%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245,0.1%, 618,0.3% and DSTP0.3% in super mixer, under room temperature state, do to mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 6
With the PBT weight ratio be 53.0%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245,0.2%, 618,0.2% and DSTP0.1% in super mixer, under room temperature state, do to mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 7
With the PBT weight ratio be 52.9%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245,0.2%, 618,0.2% and DSTP0.2% in super mixer, under room temperature state, do to mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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 8
With the PBT weight ratio be 52.8%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5%, 245,0.2%, 618,0.2% and DSTP0.3% in super mixer, under room temperature state, do to mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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.
Comparative Examples 1
With the PBT weight ratio be 53.5%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5% and PTW2.5% do under room temperature state in super mixer and mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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.
Comparative Examples 2
With the PBT weight ratio be 53.0%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5% and 245,0.5% 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, through 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.
Comparative Examples 3
With the PBT weight ratio be 53.0%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5% and 618,0.5% 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, through 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.
Comparative Examples 4
With the PBT weight ratio be 53.0%, decabromodiphenyl oxide 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5% and DSTP0.5% do under room temperature state in super mixer and mix, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 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.
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 test of material combustion performance is undertaken by UL-94, and specimen size is 127*12.7*3.2mm.
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 combustionproperty of material is divided into V-0 according to UL-94, V-1, the several grades of V-2 and HB.In addition, thermo-stabilizer is also passed judgment on according to the situation that obtained bill of material complexion becomes the influence of material." oyster white " represents colourless change, illustrates that the stabilizer function effect is good; The slightly coloured change of " light gray " expression, description effect is still good; " grey " expression look becomes more serious, and description effect is relatively poor; " tawny " expression look becomes serious, substantially to no effect.
The prescription of embodiment 1-8 and Comparative Examples 1-4 and every The performance test results be each table as follows:
Table 1 embodiment 1-8 prescription and material property table
| The matrix material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| PBT(％) | 53.2 | 53.1 | 53.0 | 52.9 | 52.8 | 53.0 | 52.9 | 52.8 |
| Decabromodiphenyl oxide (%) | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Antimonous oxide (%) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Tetrafluoroethylene (%) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| PTW(％) | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| Thermal oxidation stabilizer 245 (%) | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.2 | 0.2 | 0.2 |
| Thermal oxidation stabilizer 648 (%) | 0.1 | 0.2 | 0.3 | 0.3 | 0.3 | 0.2 | 0.2 | 0.2 |
| Thermal oxidation stabilizer DSTP (%) | 0.1 | 0.1 | 0.1 | 0.2 | 0.3 | 0.1 | 0.2 | 0.3 |
| Glass fibre (%) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Heat-drawn wire (1.82MPa) (℃) | 207 | 208 | 208 | 210 | 210 | 210 | 210 | 210 |
| Unnotched impact strength (kJ/m 2) | 36 | 38 | 38 | 36 | 35 | 45 | 42 | 37 |
| Tensile strength (MPa) | 108 | 108 | 110 | 105 | 106 | 115 | 114 | 109 |
| Elongation at break (%) | 1.8 | 2.0 | 2.2 | 2.0 | 2.0 | 2.5 | 2.5 | 2.1 |
| Flexural strength (MPa) | 170 | 170 | 172 | 171 | 173 | 178 | 177 | 177 |
| Modulus in flexure (MPa) | 9500 | 11000 | 11000 | 11500 | 11200 | 12500 | 12600 | 12500 |
| Flame-retarding characteristic | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| The bill of material complexion becomes | Light gray | Light gray | Milky white | Milky white | Milky white | Milky white | Milky white | Milky white |
Data analysis from each embodiment of table 1, in this system of glass flame-retardant reinforced PBT, the composite one side of stablizer has very big influence to the performance of material, on the other hand also and do not mean that the addition of stablizer is big more, the processing heat stability of material can just can be protected more, thereby can the good material of obtained performance.Reasonably the stablizer compound proportion just can reach this purpose.Passable the going out of data from table, in this system, this desired proportions is: 245: 648: DSTP=0.2: 0.2: 0.1
Table 2 Comparative Examples 1-4 prescription and material property table
| The matrix material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PBT(％) | 53.5 | 53.0 | 53.0 | 53.0 |
| Decabromodiphenyl oxide (%) | 10 | 10 | 10 | 10 |
| Antimonous oxide (%) | 3.5 | 3.5 | 3.5 | 3.5 |
| Tetrafluoroethylene (%) | 0.5 | 0.5 | 0.5 | 0.5 |
| PTW(％) | 2.5 | 2.5 | 2.5 | 2.5 |
| Thermal oxidation stabilizer 245 (%) | - | 0.5 | - | - |
| Thermal oxidation stabilizer 648 (%) | - | - | 0.5 | - |
| Thermal oxidation stabilizer DSTP (%) | - | - | - | 0.5 |
| Glass fibre (%) | 30 | 30 | 30 | 30 |
| Heat-drawn wire (1.82MPa) (℃) | 200 | 207 | 205 | 203 |
| Unnotched impact strength (kJ/m 2) | 30 | 38 | 36 | 34 |
| Tensile strength (MPa) | 94 | 110 | 106 | 105 |
| Elongation at break (%) | 1.8 | 2.5 | 2.2 | 2.0 |
| Flexural strength (MPa) | 155 | 168 | 165 | 160 |
| Modulus in flexure (MPa) | 8500 | 11000 | 10500 | 10000 |
| Flame-retarding characteristic | V-0 | V-0 | V-0 | V-0 |
| The bill of material complexion becomes | Tawny | Grey | Grey | Grey |
Can see comprehensively that from table 1 embodiment and table 2 Comparative Examples in this system of glass flame-retardant reinforced PBT, the composite performance impact to material of stablizer is very remarkable.Comparative Examples 1 is under the situation that does not add any stablizer, and the overall performance of material all descends very serious, and the surface color of material has also become tawny.This obviously is because serious degraded has taken place in the course of processing PBT base-material in the system.By the data of Comparative Examples 2～4 and the data declaration of embodiment, single certain stablizer neither be very desirable to the hot-work stability action effect of material, the impact strength decreased that is reflected in material significantly is also very big, and the color of material surface grey still.
Claims (9)
1. an anti-look becomes, has the halogen combustion-proof glass fiber to strengthen the polybutylene terephthalate matrix material, comprise glass fibre, polybutylene terephthalate, it is characterized in that, mixed type thermo-stabilizer, decabromodiphenyl oxide, antimonous oxide, tetrafluoroethylene, toughness reinforcing and compatilizer in described polybutylene terephthalate matrix material, have been added, described mixed type thermo-stabilizer is thermal oxidation stabilizer 245, thermal oxidation stabilizer 618 and thermal oxidation stabilizer DSTP, and each component is mixed with by following weight percentage % proportion raw material:
Polybutylene terephthalate 45-75
Decabromodiphenyl oxide 8-15
Antimonous oxide 3-5
Tetrafluoroethylene 0.2-1
Toughness reinforcing and compatilizer 1.5-20
Thermal oxidation stabilizer 245 0.1-2
Thermal oxidation stabilizer 618 0.1-2
Thermal oxidation stabilizer DSTP 0.1-2
Glass fibre 10-37
Wherein, described toughness reinforcing and compatilizer is a kind of ethylene copolymer that contains epoxy-functional.
2. a kind of anti-look according to claim 1 becomes, has the halogen combustion-proof glass fiber to strengthen the polybutylene terephthalate matrix material, it is characterized in that, described polybutylene terephthalate 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 anti-look according to claim 1 becomes, has the halogen combustion-proof glass fiber to strengthen the polybutylene terephthalate matrix material, it is characterized in that, described decabromodiphenyl oxide is melt temperature 290-310 ℃, heat decomposition temperature＞310 ℃, bromine content＞82%, the white powder of particle diameter 5-10 micron.
4. a kind of anti-look according to claim 1 becomes, has the halogen combustion-proof glass fiber to strengthen the polybutylene terephthalate matrix material, it is characterized in that, described antimonous oxide is melt temperature 650-660 ℃, decomposition temperature 1450-1460 ℃, and particle diameter 1500 purpose white powders.
5. a kind of anti-look according to claim 1 becomes, has the halogen combustion-proof glass fiber to strengthen the polybutylene terephthalate matrix material, it is characterized in that described tetrafluoroethylene is a particle diameter 5-10 micron, apparent density 250-300g/l, fusing point 320-330 ℃.
6. a kind of anti-look according to claim 1 becomes, has the halogen combustion-proof glass fiber to strengthen the polybutylene terephthalate matrix material, it is characterized in that described glass fiber diameter is the 6-17 micron.
7. a kind of anti-look according to claim 1 becomes, has the halogen combustion-proof glass fiber to strengthen the preparation method of polybutylene terephthalate matrix material, it is characterized in that its method is as follows:
(1) each component by weight percentage composition weigh raw material;
(2) glass fibre is handled through silane coupling agent;
(3) with polybutylene terephthalate, decabromodiphenyl oxide, antimonous oxide, tetrafluoroethylene, toughness reinforcing and compatilizer, thermal oxidation stabilizer 245, thermal oxidation stabilizer 618 and thermal oxidation stabilizer DSTP dried mixing 3-5 minute in super mixer;
(4) raw materials mixed is placed dual-screw-stem machine with the glass fibre blending, 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.
8. a kind of anti-look according to claim 7 becomes, there is the halogen combustion-proof glass fiber to strengthen the preparation method of polybutylene terephthalate 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, a kind of in N-phenyl-gamma-amino propyl trimethoxy silicane and the γ-r-chloropropyl trimethoxyl silane.
9. a kind of anti-look according to claim 8 becomes, has the halogen combustion-proof glass fiber to strengthen the preparation method of polybutylene terephthalate matrix material, it is characterized in that described silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.
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| CN101225220B (en) * | 2007-12-25 | 2011-08-31 | 南通市东方实业有限公司 | Flame-retardant reinforced polybutylene terephthalate compound and production method thereof |
| CN101469106B (en) * | 2007-12-25 | 2012-09-05 | 上海普利特复合材料股份有限公司 | Flame-retardant reinforced PBT composition |
| CN101633774B (en) * | 2009-08-28 | 2012-04-25 | 金发科技股份有限公司 | PBT molding composite and preparation method thereof |
| CN104497351B (en) * | 2014-12-14 | 2018-09-04 | 天津利安隆新材料股份有限公司 | Anti-oxidant compositions and its application in preparing factice for filling cables |
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