CN103819882B - Halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof - Google Patents
Halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof Download PDFInfo
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- CN103819882B CN103819882B CN201210464048.9A CN201210464048A CN103819882B CN 103819882 B CN103819882 B CN 103819882B CN 201210464048 A CN201210464048 A CN 201210464048A CN 103819882 B CN103819882 B CN 103819882B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- 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 claims abstract description 24
- 239000011159 matrix material Substances 0.000 title claims abstract description 22
- 239000011152 fibreglass Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000007654 immersion Methods 0.000 claims abstract description 45
- 239000003365 glass fiber Substances 0.000 claims abstract description 30
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 12
- -1 acryl functional group Chemical class 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920001897 terpolymer Polymers 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
- 238000012360 testing method Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 27
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of halogen-free flame-retardant long fiber glass reinforced PBT matrix material, be made up of following each component by total weight percent: PBT? 42 ~ 72.5%, toughner 2 ~ 6%, halogen-free flame retardants 10 ~ 20%, thermo-stabilizer 0.5 ~ 2.0% and long glass fibres 15 ~ 30%; Wherein said long glass fibres is PBT special LFT alkali-free continuous long glass fiber.The material that the present invention prepares gained has high workability, excellent thermotolerance, high rigidity, HI high impact, high-dimensional stability, excellent flame retardant properties and high CTI value, its tensile strength>=90MPa, modulus in flexure>=6000MPa, notched Izod impact strength>=15KJ/m after testing
2, heat-drawn wire (1.80Mpa)>=200 DEG C, does flame retardant rating reach UL94? 1.6mmV-0, CTI value>=500V, and the present invention adopts the technology of the two melt immersion slot series connection of high/low temperature to solve the shortcoming of halogen-free flame retardants pyrolytic decomposition.<!--1-->
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant polymer matrix material, particularly relate to a kind of halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof.
Background technology
Glass fiber reinforced polybutylene terephthalate (PBT) product has excellent electrical property and every integrated application performance, is widely used in the fields such as electric.Along with the raising day by day of entire society's Environmental awareness, halogen-free flameproof becomes the main flow of fiber glass reinforced PBT technical development.But fiber glass reinforced PBT will reach V-0 grade non-halogen flame-retardant to be needed to add a lot of halogen-free flame retardants, this can the serious mechanical property, particularly notched Izod impact strength reducing the material of fiber glass reinforced PBT.If the enhancing glass of fire retardant PBT with no halogen adopts continuous long glass fiber to obtain continuous long glass fiber reinforced PBT composite (LFTPBT), then its mechanical property just can General Promotion, just the high performance of fire retardant PBT with no halogen can be realized, but due in LFTPBT production process for ensure PBT to the effect of impregnation of continuous long glass fiber, very high (>=300 DEG C) that the melt temperature of PBT is arranged usually, and under high temperature, the decomposition of halogen-free flame retardants is very serious.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof, this matrix material is by adopting continuous long glass fiber reinforced, make fire retardant PBT with no halogen high performance, and improve existing preparation technology, solve the shortcoming of halogen-free flame retardants pyrolytic decomposition in impregnation process.
The present invention in order to the technical scheme solving its technical problem and adopt is:
A kind of halogen-free flame-retardant long fiber glass reinforced PBT matrix material, is made up of following each component by total weight percent:
PBT42~72.5%
Toughner 2 ~ 6%
Halogen-free flame retardants 10 ~ 20%
Thermo-stabilizer 0.5 ~ 2.0%
Long glass fibres 15 ~ 30%;
The relative viscosity of wherein said PBT is 0.8 ~ 1.0, and described long glass fibres is PBT special LFT alkali-free continuous long glass fiber.
Its further technical scheme is:
Described thermo-stabilizer is at least one in phenols, the mixture class of acryl functional group and monothioester, phosphorous acid esters, half Hinered phenols, amine and calixarene, and its effect is the degraded suppressing to produce in the course of processing.
Described toughner is polar monomer graft polymkeric substance, and wherein polymkeric substance is at least one in the multipolymer of polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, vinylbenzene and divinyl, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer; Polar monomer is can at least one in the anhydrides monomer of double-bond polymerization, acrylic monomer and acrylic ester monomer; Its effect is the PBT impact strength decreased caused to improve halogen-free flame retardants.
Described can the anhydrides monomer of double-bond polymerization be at least one in maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride and vinyl Succinic anhydried; Described acrylic monomer is at least one in vinylformic acid and methacrylic acid; Described acrylic ester monomer is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate and glytidyl methacrylate.
Described halogen-free flame retardants is at least one in organic hypophosphite, melamine polyphosphate and melamine cyanurate.
Present invention also offers a kind of preparation method of halogen-free flame-retardant long fiber glass reinforced PBT matrix material, comprise the following steps:
(1) be transported to high-temperature fusant immersion slot by mouth mould after being plastified by single screw extrusion machine by 20 ~ 50wt.% of described PBT total amount, in the groove of described high-temperature fusant immersion slot, temperature is 300-360 DEG C, and described high-temperature fusant immersion slot length is 2 ~ 2.5m;
(2) low-temperature melt immersion slot is transported to remaining described in (1) after PBT, 0.5 ~ 2.0wt.% thermo-stabilizer, 2 ~ 6wt.% toughner and 10 ~ 20wt.% halogen-free flame retardants are plastified by single screw extrusion machine by mouth mould, in the groove of described low-temperature melt immersion slot, temperature is 230 ~ 250 DEG C, and described low-temperature melt immersion slot length is 1 ~ 1.5m;
(3) 15 ~ 30wt.% long glass fibres is entered the high-temperature fusant immersion slot in (1) and the low-temperature melt immersion slot in (2) successively with the speed drawing of 25 ~ 70m/min; to be infiltrated by traction and after cooling, the special dicing machine of employing LFT cuts into the long particle of 12mm.
Advantageous Effects of the present invention is: the present invention is strengthened by continuous long glass fiber makes fire retardant PBT with no halogen high performance, adopt high simultaneously, the production technique of low-temperature melt immersion slot series connection, realize first realizing the infiltration of part PBT resin to long glass fibres in high-temperature fusant immersion slot, then in low-temperature melt, in immersion slot, coated one deck PBT adds the skin of halogen-free flame retardants, final product is internal layer is that PBT infiltrates long glass fibres master batch, skin is the mixture of PBT and halogen-free flame retardants, ectonexine can realize abundant dispersion in later product injection moulding process, under this technology effectively can solve the condition of high temperature, PBT halogen-free flame retardants decomposes serious defect.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but the present invention is not limited to following embodiment.
Embodiment one:
The first step: by 15 kilograms of PBT1200M by being transported to high-temperature fusant immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described high-temperature fusant immersion slot, temperature is 300 DEG C, and described high-temperature fusant immersion slot length is 2m;
Second step: by 57.5 kilograms of PBT1200M, 2 kilograms of toughner EVA2825,0.2 kilogram of phenolic thermostabilizers, 1010,0.3 kilogram of phosphite antioxidant, 168,10 kilograms of Ke Laien fire retardant OP1311 by being transported to low-temperature melt immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described low-temperature melt immersion slot, temperature is 230 DEG C, and described low-temperature melt immersion slot length is 1m;
3rd step: 15 kilograms of PPG companies are produced continuous long glass fiber Tufrov4585 with the high-temperature fusant groove of 25mm/min speed successively in the first step and the low-temperature melt groove in second step; after long glass fibres draws and infiltrates from melt tank; the long homogeneous particle of 12mm is cut into the special dicing machine of LFT; obtain composite A, its performance is as shown in table 1:
The performance of table 1 composite A
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm 3 | ISO 1183 | 1.50 |
| Glass fiber content (750 DEG C, 30min) | % | ISO 3451/1 | 15 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 206 |
| Tensile strength | MPa | ISO527/2-93 | 115 |
| Modulus in flexure | MPa | ISO178/2-93 | 6500 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 16.5 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 600 |
Embodiment two:
The first step: by 20 kilograms of PBT1100L by being transported to high-temperature fusant immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described high-temperature fusant immersion slot, temperature is arranged on 320 DEG C, and described high-temperature fusant immersion slot length is 2m;
Second step: by 40 kilograms of PBT1200M, 4 kilograms of toughner PTW, 0.5 kilogram of phenolic thermostabilizers, 1010,0.5 kilogram of phosphite antioxidant 627A, 15 kilograms of Ke Laien fire retardant OP1312 by being transported to low-temperature melt immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described low-temperature melt immersion slot, temperature is 240 DEG C, and described low-temperature melt immersion slot length is 1m;
3rd step: 20 kilograms of PPG companies are produced continuous long glass fiber Tufrov4585 with the high-temperature fusant groove of 50mm/min speed successively in the first step and the low-temperature melt groove in second step; after long glass fibres draws and infiltrates from melt tank; the long homogeneous particle of 12mm is cut into dicing machine; obtain matrix material B, its performance is as shown in table 2:
The performance of table 2 matrix material B
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm 3 | ISO 1183 | 1.55 |
| Glass fiber content (750 DEG C, 30min) | % | ISO 3451/1 | 20 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 210 |
| Tensile strength | MPa | ISO527/2-93 | 130 |
| Modulus in flexure | MPa | ISO178/2-93 | 7200 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 18.5 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 600 |
Embodiment three:
The first step: by 20 kilograms of PBT4115 by being transported to high-temperature fusant immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described high-temperature fusant immersion slot, temperature is 340 DEG C, and described high-temperature fusant immersion slot length is 2.5m;
Second step: by 33.5 kilograms of PBT4115,5 kilograms of toughner PTW, 0.8 kilogram of phenolic thermostabilizers, 1010,0.7 kilogram of phosphite antioxidant 627A, 10 kilograms of Ke Laien fire retardant OP1240,5 kilograms of fire-retartant agent MP P by being transported to low-temperature melt immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described low-temperature melt immersion slot, temperature is arranged on 245 DEG C, and described low-temperature melt immersion slot length is 1.5m;
3rd step: 25 kilograms of PPG companies are produced continuous long glass fiber Tufrov4588 with the high-temperature fusant groove of 70mm/min speed successively in the first step and the low-temperature melt groove in second step; after long glass fibres draws and infiltrates from melt tank; the long homogeneous particle of 12mm is cut into dicing machine; obtain matrix material C, its performance is as table
Shown in 3:
The performance of table 3 matrix material C
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm 3 | ISO 1183 | 1.58 |
| Glass fiber content (750 DEG C, 30min) | % | ISO 3451/1 | 25 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 212 |
| Tensile strength | MPa | ISO527/2-93 | 140 |
| Modulus in flexure | MPa | ISO178/2-93 | 8000 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 17.5 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 550 |
Embodiment four:
The first step: by 20 kilograms of PBT5215G by being transported to high-temperature fusant immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described high-temperature fusant immersion slot, temperature is arranged on 360 DEG C, and described high-temperature fusant immersion slot length is 2.3m;
Second step: by 22 kilograms of PBT5215G, 6 kilograms of toughner PTW, 1 kilogram of phenolic thermostabilizers, 1010,1 kilogram of monothioester oxidation inhibitor 412S, 15 kilograms of Ke Laien fire retardant OP1230,5 kilograms of fire retardant MCA by being transported to low-temperature melt immersion slot by mouth mould after the plasticizing of length-to-diameter ratio 20:1 single screw extrusion machine, in the groove of described low-temperature melt immersion slot, temperature is arranged on 250 DEG C, and described low-temperature melt immersion slot length is 1.3m;
3rd step: 30 kilograms of PPG companies are produced continuous long glass fiber Tufrov4588 with the high-temperature fusant groove of 70mm/min speed successively in the first step and the low-temperature melt groove in second step; after long glass fibres draws and infiltrates from melt tank; the long homogeneous particle of 12mm is cut into dicing machine; obtain matrix material D, its performance is as shown in table 4:
The performance of table 4 matrix material D
| Performance | Unit | Testing standard | Test result |
| Density (23 DEG C) | g/cm 3 | ISO 1183 | 1.63 |
| Glass fiber content (750 DEG C, 30min) | % | ISO 3451/1 | 30 |
| HDT（1.80MPa） | ℃ | ISO75/1-93 | 215 |
| Tensile strength | MPa | ISO527/2-93 | 150 |
| Modulus in flexure | MPa | ISO178/2-93 | 8800 |
| Notched Izod impact strength | KJ/m 2 | ISO179/2-93 | 17.5 |
| Flame retardant resistance | -- | UL94 | 1.6mmV-0 |
| CTI value | V | IEC 60112 | 500 |
Can be found out by above-described embodiment, the material that the present invention prepares gained has high workability, excellent thermotolerance, high rigidity, HI high impact, high-dimensional stability, excellent flame retardant properties and high CTI value, its tensile strength>=90MPa, modulus in flexure>=6000MPa, notched Izod impact strength>=15KJ/m after testing
2, heat-drawn wire (1.80Mpa)>=200 DEG C, flame retardant rating reaches UL941.6mmV-0, CTI value>=500V, and the present invention adopts the technology of the two melt immersion slot series connection of high/low temperature to solve the shortcoming of halogen-free flame retardants pyrolytic decomposition.
Above embodiment is only exemplary embodiment of the present invention, and be not used in restriction the present invention, protection scope of the present invention is defined by the claims.Those skilled in the art can in essence of the present invention and protection domain, and make various amendment or equivalent replacement to the present invention, this amendment or equivalent replacement also should be considered as dropping in protection scope of the present invention.
Claims (6)
1. a preparation method for halogen-free flame-retardant long fiber glass reinforced PBT matrix material, is characterized in that: comprise the following steps:
(1) high-temperature fusant immersion slot is transported to by mouth mould after being plastified by single screw extrusion machine by 20 ~ 50wt.% of formula consumption PBT total amount, in the groove of described high-temperature fusant immersion slot, temperature is 300-360 DEG C, and described high-temperature fusant immersion slot length is 2 ~ 2.5m;
(2) residue PBT, 0.5 ~ 2.0wt.% thermo-stabilizer, 2 ~ 6wt.% toughner and 10 ~ 20wt.% halogen-free flame retardants in (1) is transported to low-temperature melt immersion slot by mouth mould after being plastified by single screw extrusion machine, in the groove of described low-temperature melt immersion slot, temperature is 230 ~ 250 DEG C, and described low-temperature melt immersion slot length is 1 ~ 1.5m;
(3) 15 ~ 30wt.% long glass fibres is entered the high-temperature fusant immersion slot in (1) and the low-temperature melt immersion slot in (2) successively with the speed drawing of 25 ~ 70m/min; to be infiltrated by traction and after cooling, the special dicing machine of employing LFT cuts into the long particle of 12mm.
2. the preparation method of halogen-free flame-retardant long fiber glass reinforced PBT matrix material according to claim 1, is characterized in that: each component used in step (1), (2) and (3) is respectively by the consumption of halogen-free flame-retardant long fiber glass reinforced PBT matrix material total weight percent:
The relative viscosity of wherein said PBT is 0.8 ~ 1.0, and described long glass fibres is PBT special LFT alkali-free continuous long glass fiber.
3. the preparation method of halogen-free flame-retardant long fiber glass reinforced PBT matrix material according to claim 2, is characterized in that: described thermo-stabilizer is at least one in phenols, the mixture class of acryl functional group and monothioester, phosphorous acid esters, half Hinered phenols, amine and calixarene.
4. the preparation method of halogen-free flame-retardant long fiber glass reinforced PBT matrix material according to claim 2, it is characterized in that: described toughner is polar monomer graft polymkeric substance, wherein polymkeric substance is at least one in the multipolymer of polyethylene, polypropylene, vinylbenzene and divinyl, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer; Polar monomer is can at least one in the anhydrides monomer of double-bond polymerization, acrylic monomer and acrylic ester monomer.
5. the preparation method of halogen-free flame-retardant long fiber glass reinforced PBT matrix material according to claim 4, is characterized in that: described can the anhydrides monomer of double-bond polymerization be at least one in maleic anhydride, citraconic anhydride and vinyl Succinic anhydried; Described acrylic monomer is at least one in vinylformic acid and methacrylic acid; Described acrylic ester monomer is at least one in methyl acrylate, ethyl propenoate, methyl methacrylate and glytidyl methacrylate.
6. the preparation method of halogen-free flame-retardant long fiber glass reinforced PBT matrix material according to claim 1, is characterized in that: described halogen-free flame retardants is at least one in organic hypophosphite, melamine polyphosphate and melamine cyanurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210464048.9A CN103819882B (en) | 2012-11-16 | 2012-11-16 | Halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210464048.9A CN103819882B (en) | 2012-11-16 | 2012-11-16 | Halogen-free flame-retardant long fiber glass reinforced PBT matrix material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN103819882A CN103819882A (en) | 2014-05-28 |
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| CN105647130A (en) * | 2014-11-10 | 2016-06-08 | 合肥杰事杰新材料股份有限公司 | Glass fiber reinforced rigidity-and-toughness-balanced polyester composition and preparation method thereof |
| CN105385119B (en) * | 2015-11-24 | 2016-12-14 | 金发科技股份有限公司 | A kind of fiberglass reinforced fire retardant PBT composition and preparation method thereof |
| CN106566241A (en) * | 2016-11-04 | 2017-04-19 | 马鞍山市华能电力线路器材有限责任公司 | Insulation flame-retardant glass fiber reinforced PA66/PPS/PES power fitting material and preparation method thereof |
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| CN1488674A (en) * | 2002-10-09 | 2004-04-14 | 上海杰事杰新材料股份有限公司 | Long-fiber reinforced polyethylene glycol terephthalate material |
| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN101003666A (en) * | 2007-01-09 | 2007-07-25 | 南通星辰合成材料有限公司 | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method |
| CN102775744A (en) * | 2012-07-05 | 2012-11-14 | 佛山市顺德区顺炎塑料有限公司 | Environment-friendly polybutylece terephthalate (PBT) engineering plastic and preparation method thereof |
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| CN1488674A (en) * | 2002-10-09 | 2004-04-14 | 上海杰事杰新材料股份有限公司 | Long-fiber reinforced polyethylene glycol terephthalate material |
| CN1810862A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN101003666A (en) * | 2007-01-09 | 2007-07-25 | 南通星辰合成材料有限公司 | Super high flowing, white, fire retardant PBT with no halogen, in high thermal stability, and preparation method |
| CN102775744A (en) * | 2012-07-05 | 2012-11-14 | 佛山市顺德区顺炎塑料有限公司 | Environment-friendly polybutylece terephthalate (PBT) engineering plastic and preparation method thereof |
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