CN101007894B - PBT and ABS flame-proof material - Google Patents
PBT and ABS flame-proof material Download PDFInfo
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- CN101007894B CN101007894B CN2006100235341A CN200610023534A CN101007894B CN 101007894 B CN101007894 B CN 101007894B CN 2006100235341 A CN2006100235341 A CN 2006100235341A CN 200610023534 A CN200610023534 A CN 200610023534A CN 101007894 B CN101007894 B CN 101007894B
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- pbt
- abs
- fire retardant
- flame
- retardant material
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- 239000000463 material Substances 0.000 title claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 239000003063 flame retardant Substances 0.000 claims description 42
- 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 claims description 17
- 239000002994 raw material Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000002360 preparation method Methods 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
- 238000005303 weighing Methods 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims 11
- -1 polybutylene terephthalate Polymers 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052901 montmorillonite Inorganic materials 0.000 abstract 1
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a PBT and ABS flame- proof material. The component and their weight proportion are follows: 30-70% of PBT, 10-50% of ABS, 1-20% of copolymers of styrene and acrylonitrile, 1-20% of styrene-acrylonitrile copolymer graft glycidyl methacrylate, 1-20% of montmorillonite, 1-20% of flame- proof agent, 0.1-1% of anti-oxidant. The PBT/ABS flame- proof material possesses high flame- proof performance, the flame- proof grade reaching V0 class of UL 94 standard, and also improves material performance, especially the rigidity and thermal resistance. The stability of the product size is good. The inventive flame- proof material belongs to the environmental protection product, and is applicable to inject and shape electrical apparatus that requires environmental protection and flame proof.
Description
Technical field
The present invention relates to a kind of PBT and ABS fire retardant material, relate in particular to a kind of injection moulding various that the environmental protection flame retardant requirement arranged and the electronic electric equipment of usefulness and a kind of PBT and ABS nano flame retardant materials of household appliances for export of can be used for.
Technical background
The used fire retardant nearly 95% of present flame-retardant PBT/ABS is a halogen containing flame-retardant, be that brominated flame-retardant efficient height, the consumption of representative is few particularly with polybromodiphenyl ether and polybrominated biphenyl material, performance impact to material is little, and it is moderate, its usefulness/price can be equal to than non-other fire retardants, so 70%～80% all uses this based flame retardant in China's electric series products for export.But bromide fire retardant is subjected to the puzzlement of dioxin problem in recent years, use its (bromo-antimony system) fire-retardant macromolecular material the time can generate a large amount of flue dust and corrosive gases simultaneously, at present European Union and Japan this based flame retardant of use of putting into effect in succession that it is forbidden by decree in thermo-cracking and burning.European Union will rise on July 1st, 2006 and implement in full the ROHS instruction, and the electronic and electrical equipment that this decree requires to throw in European Union must not contain poly-dibromodiphenyl ether, poly-bromo biphenyl, and this decree has seriously restricted the outlet of China's electronic and electrical equipment.
Summary of the invention
The object of the present invention is to provide a kind of high efficiency flame retardance that has, good comprehensive mechanical property satisfies the environment-friendly type PBT/ABS fire retardant material of ROHS command request simultaneously.
For realizing above purpose, technical scheme of the present invention provides a kind of PBT and ABS fire retardant material, and it is made up of a mixture, and its weight proportion consists of:
PBT 30-70％、
ABS 10-50％、
The copolymer 1 of vinylbenzene and vinyl cyanide-20%,
Styrene-acrylonitrile copolymer graft glycidyl methacrylate 1-20%,
Polynite 1-20%,
Fire retardant 1-20%,
Oxidation inhibitor 0.1-1%.
Described fire retardant is the Halogen type, is phosphorus flame retardant or borate.
Wherein the relative viscosity of PBT is 0.8-1.5PaS; ABS is vinyl cyanide, divinyl and styrene copolymer, and its rubber content is 35%-70%; The melting index of the multipolymer of vinylbenzene and vinyl cyanide is 15-40g/10min; The styrene-acrylonitrile copolymer graft glycidyl methacrylate is the styrene-acrylonitrile copolymer graft glycidyl methacrylate; Polynite is a kind of silicate clay that has passed through the laminate structure of organic modification, and average wafer thickness is less than 30 nanometers, and is brilliant in the 1-5 nanometer; Described oxidation inhibitor is 1076 Hinered phenols antioxidants, or the compound system of Hinered phenols antioxidant 1010 and phosphite ester kind antioxidant 168, and wherein 1010 and 168 compound proportion is 1: 1.
The preparation method of PBT and ABS fire retardant material is characterized in that, its method is as follows:
(1) takes by weighing raw material by weight ratio;
(2) all raw materials are put into high-speed mixer and mixing 2-5 minute;
(3) discharging;
(4) raw materials mixed is put into screw rod machine extruding pelletization, the rotating speed of screw rod machine is 180-600 rev/min, and temperature is 230-260 ℃.
The PBT content of carboxyl end group that the present invention adopts is low, and hydrolytic resistance is good; Crystallization velocity is fast, easy-formation; Fusing point is higher, and thermotolerance is good; Water-intake rate is low, and dimensional stability is good; Frictional coefficient is low, abrasion performance; Chemicals-resistant, solvent borne are good.
The ABS rubber powder that the present invention adopts has outstanding tough, high glossiness, formability and resistance to chemical reagents.
The present invention adopts PBT/ABS as matrix resin, make a kind of PBT and ABS nano flame retardant material, solve fire retardant well to the influence of PBT/ABS mechanical property and resistance toheat and the feature of environmental protection problem of flame-retardant PBT/ABS, prepared a kind of have dimensional stabilizing, good toughness, intensity height, good, the easy processing of outward appearance, resistance to chemical reagents, PBT and ABS nano flame retardant material that density is lower.
Advantage of the present invention is to utilize the synergistic effect of polynite and halogen-free flame retardants, has not only abandoned traditional bromo-antimony flame-retardant system, has excellent flame-retardant and mechanical property, does not endanger environment and health of human body, belongs to environmentfriendly products; And using polynite to reduce the usage quantity of fire retardant, this has improved the mechanical property and the resistance toheat of fire retardant material to a great extent, the more important thing is greatly to reduce production costs.
Specific embodiments
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1-3:
With PBT/ABS is matrix resin, and the styrene-acrylonitrile copolymer graft glycidyl methacrylate is a compatilizer, is fire retardant with TPP, adds polynite, and 1098/168 (1: 1) and 1076 is an oxidation inhibitor.
Proportioning 1-3
Whole components were put into high-speed mixer and mixing 4 minutes in proportion, use the screw extrusion press extruding pelletization then, processing temperature is at 240 ℃.
Sample that makes according to embodiment 1-3 and the contrast of traditional bromo-antimony flame-retardant system:
Mechanics Performance Testing is according to the ASTM standard, and flame retardant properties is tested according to the UL94 standard.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Bromo-antimony flame-retardant system |
| Tensile strength Mpa | 50 | 45 | 45 | 45 |
| Flexural strength Mpa | 70 | 62 | 58 | 60 |
| Modulus in flexure Mpa | 2500 | 2200 | 1900 | 1800 |
| Shock strength J/M | 300 | 200 | 1800 | 180 |
| 3.2mm it is fire-retardant | V0 | V0 | V0 | V0 |
Claims (7)
1. PBT and ABS fire retardant material is characterized in that it is made up of a mixture, and its weight proportion consists of:
PBT 30-70％、
ABS 10-50％、
The copolymer 1 of vinylbenzene and vinyl cyanide-20%,
Styrene-acrylonitrile copolymer graft glycidyl methacrylate 1-20%
Polynite 1-20%,
Fire retardant 1-20%,
Oxidation inhibitor 0.1-1%;
Described fire retardant is the Halogen type, is phosphorus flame retardant or borate.
2. PBT according to claim 1 and ABS fire retardant material is characterized in that, described PBT is a polybutylene terephthalate, and wherein the relative viscosity of PBT is 0.8-1.5PaS, and melt temperature is 225-240 ℃.
3. PBT according to claim 1 and ABS fire retardant material is characterized in that, described ABS is vinyl cyanide, divinyl and styrene copolymer, and its rubber content is 35%-70%, and relative density is 1.0-1.04, and melt temperature is 190-220 ℃.
4. PBT according to claim 1 and ABS fire retardant material is characterized in that, the melting index of the multipolymer of described vinylbenzene and vinyl cyanide is 15-40g/10min.
5. PBT according to claim 1 and ABS fire retardant material is characterized in that, described polynite is a kind of silicate clay that has passed through the laminate structure of organic modification, and average wafer thickness is less than 30 nanometers, and is brilliant in the 1-5 nanometer.
6. PBT according to claim 1 and ABS fire retardant material, it is characterized in that, described oxidation inhibitor is the compound system of 1076 Hinered phenols antioxidants or Hinered phenols antioxidant 1010 and phosphite ester kind antioxidant 168, and wherein 1010 and 168 compound proportion is 1: 1.
7. the preparation method of PBT according to claim 1 and ABS fire retardant material is characterized in that, its method is as follows:
(1) takes by weighing raw material by weight ratio;
(2) all raw materials are put into high-speed mixer and mixing 2-5 minute;
(3) discharging;
(4) raw materials mixed is put into screw rod machine extruding pelletization, the rotating speed of screw rod machine is 180-600 rev/min, and temperature is 230-260 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100235341A CN101007894B (en) | 2006-01-23 | 2006-01-23 | PBT and ABS flame-proof material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100235341A CN101007894B (en) | 2006-01-23 | 2006-01-23 | PBT and ABS flame-proof material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101007894A CN101007894A (en) | 2007-08-01 |
| CN101007894B true CN101007894B (en) | 2011-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100235341A Expired - Fee Related CN101007894B (en) | 2006-01-23 | 2006-01-23 | PBT and ABS flame-proof material |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280098B (en) * | 2008-05-20 | 2011-07-20 | 上海大学 | Halogen-free flame-proof strengthened polyethylene glycol terephthalate engineering plastics and preparation thereof |
| CN101654547B (en) * | 2009-09-24 | 2012-07-18 | 威海联桥新材料科技股份有限公司 | Solid condensation-type organic phosphate flame-retardant PBT/ABS alloy material and preparation method thereof |
| CN101787192B (en) * | 2009-10-15 | 2012-05-30 | 上海锦湖日丽塑料有限公司 | Low-gloss polycarbonate styrene resin composition and preparation method thereof |
| CN102108187B (en) * | 2009-12-28 | 2012-09-12 | 上海日之升新技术发展有限公司 | High glowing filament environmental-friendly inflaming retarding reinforced polybutylece terephthalate (PBT)/acrylonitrile butadiene styrene (ABS) alloy material and preparation method thereof |
| CN102477214A (en) * | 2010-11-23 | 2012-05-30 | 上海锦湖日丽塑料有限公司 | Thermoplastic polyester composition containing recycled slag and preparation method thereof |
| CN102352088A (en) * | 2011-09-07 | 2012-02-15 | 金发科技股份有限公司 | Thermoplastic halogen-free flame-retardant alloy and preparation method thereof |
| CN102367322A (en) * | 2011-10-17 | 2012-03-07 | 常熟市星源金属涂层厂 | ABS (acrylonitrile butadiene styrene) halogen-free flame-retardant composite material and preparation method thereof |
| CN103013066B (en) * | 2012-12-14 | 2014-12-10 | 上海锦湖日丽塑料有限公司 | High face impact PET/ABS (polyethylene Terephthalate/acrylonitrile-butadiene-styrene) halogen-free flame retardant alloy and preparation method thereof |
| CN104403292B (en) * | 2014-11-28 | 2016-06-29 | 上海锦湖日丽塑料有限公司 | A kind of can the resin combination and preparation method thereof of direct water transfer |
| CN109749347A (en) * | 2018-12-27 | 2019-05-14 | 会通新材料股份有限公司 | A kind of resistance to grease ABS composite material of low linear expansion coefficient and preparation method thereof |
| KR20240138877A (en) * | 2023-03-13 | 2024-09-20 | 롯데케미칼 주식회사 | Thermoplastic resin composition and molded article using the same |
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|---|---|---|---|---|
| EP0491985B1 (en) * | 1990-12-24 | 2000-08-02 | General Electric Company | Impact modified polybutylene terephthalate |
| CN1396207A (en) * | 2001-07-11 | 2003-02-12 | 汎塑料株式会社 | Flame-retarded resin composition and its forming product |
| US6531530B2 (en) * | 1999-12-28 | 2003-03-11 | Daicel Chemical Industries, Ltd. | Non halogen, organic or inorganic flame retardants in thermoplastic polymer blends |
-
2006
- 2006-01-23 CN CN2006100235341A patent/CN101007894B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0491985B1 (en) * | 1990-12-24 | 2000-08-02 | General Electric Company | Impact modified polybutylene terephthalate |
| US6531530B2 (en) * | 1999-12-28 | 2003-03-11 | Daicel Chemical Industries, Ltd. | Non halogen, organic or inorganic flame retardants in thermoplastic polymer blends |
| CN1396207A (en) * | 2001-07-11 | 2003-02-12 | 汎塑料株式会社 | Flame-retarded resin composition and its forming product |
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| CN101007894A (en) | 2007-08-01 |
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