CN101328305B - A kind of halogen-free flame-retardant PBT/PC alloy composition and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant PBT/PC alloy composition and preparation method thereof Download PDFInfo
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- CN101328305B CN101328305B CN2008100297065A CN200810029706A CN101328305B CN 101328305 B CN101328305 B CN 101328305B CN 2008100297065 A CN2008100297065 A CN 2008100297065A CN 200810029706 A CN200810029706 A CN 200810029706A CN 101328305 B CN101328305 B CN 101328305B
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- pbt
- halogen
- magnesium hydroxide
- fire retardant
- retardant pbt
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 35
- 239000000956 alloy Substances 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 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 20
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 39
- -1 phosphate ester Chemical class 0.000 claims abstract description 29
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 23
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 238000005453 pelletization Methods 0.000 claims abstract description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 36
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 36
- 239000004593 Epoxy Substances 0.000 claims description 26
- 230000004913 activation Effects 0.000 claims description 24
- 229920003986 novolac Polymers 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 20
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 10
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- 238000007254 oxidation reaction Methods 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
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- 230000004927 fusion Effects 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
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- 238000000034 method Methods 0.000 abstract description 8
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- 229910019142 PO4 Inorganic materials 0.000 abstract 1
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- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000004843 novolac epoxy resin Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 40
- 229920000515 polycarbonate Polymers 0.000 description 37
- 239000004417 polycarbonate Substances 0.000 description 37
- 239000000178 monomer Substances 0.000 description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 8
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
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- 239000000463 material Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 150000001282 organosilanes Chemical class 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 125000003700 epoxy group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920006778 PC/PBT Polymers 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical class [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
本发明公开了一种无卤阻燃PBT/PC合金组合物及其制备方法。该组合物按质量百分比计，其配方由如下组分组成：40％～50％PBT、10％～20％PC、23％～33％活化氢氧化镁、3％～7％磷酸酯齐聚物、3％～7％聚硅氧烷/丙烯酸酯类接枝共聚物、3％～7％酚醛环氧树脂、0.2％～0.4％抗氧剂和0.4％～0.8％加工助剂。该方法是将配方中各组分分散混合后，通过双螺杆机熔融、混炼、挤出、冷却、干燥、切粒和包装。本发明将各添加组分的阻燃成炭作用以及与基体的界面相互作用相结合，使体系各组分形成缺一不可的有机整体，在较低的氢氧化镁用量下获得了较高的阻燃性能，且体系力学性能、热性能与加工性能良好。The invention discloses a halogen-free flame-retardant PBT/PC alloy composition and a preparation method thereof. In terms of mass percentage, the composition is composed of the following components: 40%-50% PBT, 10%-20% PC, 23%-33% activated magnesium hydroxide, 3%-7% phosphate ester oligomer , 3% to 7% polysiloxane/acrylate graft copolymer, 3% to 7% novolac epoxy resin, 0.2% to 0.4% antioxidant and 0.4% to 0.8% processing aid. The method comprises the steps of dispersing and mixing the components in the formulation, melting, kneading, extruding, cooling, drying, pelletizing and packaging by means of a twin-screw machine. The present invention combines the flame-retardant charring effect of each added component and the interfacial interaction with the matrix, so that each component of the system forms an indispensable organic whole, and obtains a higher Flame retardant, and the system has good mechanical properties, thermal properties and processing properties.
Description
Technical field
The present invention relates to a kind of fire retardant, particularly relate to fire retardant PBT with no halogen/PC alloy composite and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) is the fast thermoplasticity engineering materials of a kind of crystallization velocity, be easy to realize high-speed molding, has favorable rigidity and hardness, good creep properties and solvent resistance, ageing resistance and workability, water-absorbent is low, but PBT uses separately and exists product easily to shrink defectives such as deflection, heat-drawn wire are low, easy firing.Contain a large amount of phenyl ring in polycarbonate (PC) molecular chain, sterically hindered bigger, rigidity and toughness are all better, and the charring rate height can put out certainly.The self-extinguishing that a small amount of PC blending and modifying PBT (promptly forming the PBT/PC alloy) can be improved to a certain extent PBT with become the charcoal ability, and shock resistance and thermotolerance improve.The PBT/PC alloy adopts halogen and the antimonous oxide system is fire-retardant can obtain certain flame retardant resistance, but the fire-retardant anti-tracking path of alloy that makes of this method is poor, the mist that produces thick smoke during burning, and have environmental protection hidden danger, do not see open report as yet about the halogen-free flameproof of such alloy.Chinese invention patent CN1789333 discloses a kind of based on PC, and PBT is the PC/PBT alloy hoop environment friendly flame-retardant technology of assisting.This patent adopts aromatic phosphoric ester and phenmethyl silicone composite flame-retardant agent, is compatilizer with methyl methacrylate-butadiene-styrene graft copolymers (MBS) and styrene-maleic anhydride copolymer (SMAH).This alloy substrate is based on PC, its fire-retardant relatively easy realization, and compare with PC, there is tangible price advantage in PBT, therefore than the PC/PBT alloy, realizes that based on the PBT/PC alloy of PBT the value of halogen-free flameproof is bigger; In addition should invention used fire retarding synergist phenmethyl silicone and PC, PBT matrix interphase interaction power is less, is difficult to form stronger interface combination, need use a large amount of MBS, SMAH compatilizer in the system; Moreover the system all components is organic polymer material, improves unhelpful to contraction deflection, the heat-drawn wire of product.
Summary of the invention
The present invention is conceived to solve the problem that existing PBT/PC alloy flame-retarded technology field exists, and provides to have PBT/PC alloy composite a kind of Halogen, that have excellent flame retardancy energy, mechanical property, thermal characteristics and preparation method thereof.
In order to realize the foregoing invention purpose, in the technical scheme of the present invention, with PBT, PC is base material, add activation magnesium hydroxide, phosphoric acid ester oligopolymer improvement flame retardant resistance, improve the charring rate of system with polysilsesquioxane/acrylic ester graft copolymer, novolac epoxy, improve charcoal layer structure, and increase the interaction of PBT, PC, heterogeneous each component of flame-retardant system of activation magnesium hydroxide simultaneously.Concrete technical scheme is as follows:
A kind of fire retardant PBT with no halogen/PC alloy composite, by mass percentage, its prescription is made up of following component: 40%～50%PBT, 10%～20%PC, 23%～33% activation magnesium hydroxide, 3%～7% phosphoric acid ester oligopolymer, 3%～7% polysiloxane/acrylate quasi-graft copolymer, 3%～7% novolac epoxy, 0.2%～0.4% oxidation inhibitor and 0.4%～0.8% processing aid.Described activation magnesium hydroxide is for to carry out the surface-treated magnesium hydroxide with silane coupling agent, titanate coupling agent, stearic acid or stearate, and particle diameter is 0.5～10 μ m.This activation magnesium hydroxide can activate magnesium hydroxide with FM70D, the FM70A of Fushan City, Guangdong Province gold dagger-axe fire-fighting quipment company limited.
Described phosphoric acid ester oligopolymer is Resorcinol biphosphonate (RDP), hangs down poly bisphenol two (diphenyl phosphoester) (BDP).Described polysiloxane/acrylate quasi-graft copolymer is the organic polysilsesquioxane/acrylate graft copolymers of high phenyl (Si-ACR), organic polysilsesquioxane of high phenyl and polyacrylic ester mol ratio in graft copolymer is 0.8～2: 1, and the preparation method is according to application number 200710032309.9 disclosed flame-retardant interfacial modifier preparation method preparations.This method comprises the steps:
(1) successively or be added drop-wise to after mixing in the aqueous solution that is dissolved with anionic emulsifier or compound emulsifying agent with two functionality organosilanes and trialkoxy silane organosilane monomer, 30～60 ℃ were reacted 6～12 hours down, obtain the organic polysilsesquioxane emulsion of high phenyl; It is 10%～45% that two functionality organosilanes occupy machine silane monomer molecular fraction, and it is 50%～85% that trialkoxy silane occupies machine silane monomer molecular fraction; Organosilane monomer total mass is 25%～40% of a quality; The emulsifying agent consumption is 0.5%～10% of an organosilane monomer total mass, and described compound emulsifying agent is that mass ratio is 0.5～3: 1 the anionic emulsifier and the mixture of nonionic emulsifying agent;
(2) the organic polysilsesquioxane emulsion of high phenyl that step (1) is obtained is regulated pH value to 8～11 with alkaline solution, adds Sodium dodecylbenzene sulfonate emulsifying agent, initiator and acrylic ester monomer then, reacts 4～8 hours down at 50～95 ℃; Add Sodium dodecylbenzene sulfonate emulsifying agent, initiator and methyl acrylic ester monomer again, 50～95 ℃ were reacted 4～8 hours down, obtain the organic polysilsesquioxane of high phenyl/acrylate mixture emulsion, the aqueous metal salt that adds 0.5～2 times of this quality of the emulsion, 60～100 ℃ of following heating demulsification types 5～10 hours, with precipitated product cleaning, drying, obtain the organic polysilsesquioxane of high phenyl/acrylate mixture flame-retardant interfacial modifier; Wherein, the Sodium dodecylbenzene sulfonate consumption is 0.5%～5% of esters of acrylic acid or a methyl acrylic ester monomer mass; Initiator amount is 0.1%～1% of esters of acrylic acid or a methyl acrylic ester monomer mass, and adopting disposable adding or being made into mass percentage concentration is that 10% the aqueous solution drips; Methyl acrylic ester is 0.5～5: 1 with the ratio of esters of acrylic acid mole, methyl acrylic ester, both total mole numbers of esters of acrylic acid are 0.15～1.5: 1 with the ratio of organosilane total moles monomer, and feed way adopts interrupter method, semicontinuous addition method, continuous charging method or pre-emulsion process.
The epoxy functionalities of described novolac epoxy is 3.0～5.0, and the number that has epoxide group on promptly average each novolac epoxy molecule is 3.0～5.0.
Described oxidation inhibitor is phenolic antioxidant and/or phosphite ester kind antioxidant.
Described processing aid is one or more in softening agent, releasing agent, photostabilizer, pigment and the dyestuff.
The preparation method of above-mentioned fire retardant PBT with no halogen/PC alloy composite: press prescription quality per-cent, after PBT, PC, activation magnesium hydroxide, polysiloxane/acrylate quasi-graft copolymer, phosphoric acid ester oligopolymer, novolac epoxy, oxidation inhibitor and other processing aid dispersing and mixing, by the dual-screw-stem machine fusion, mixing, extrude, cool off, dry, pelletizing and packing, each subregion temperature of used double-screw extruding machine barrel remains on 230～260 ℃; By mass percentage, fire retardant PBT with no halogen/PC alloy combination composition formula is made up of following component: 40%～50%PBT, 10%～20%PC, 23%～33% activation magnesium hydroxide, 3%～7% phosphoric acid ester oligopolymer, 3%～7% polysiloxane/acrylate quasi-graft copolymer, 3%～7% novolac epoxy, 0.2%～0.4% oxidation inhibitor and 0.4%～0.8% processing aid.
The present invention adopts activation magnesium hydroxide and phosphoric acid ester oligopolymer synergistic flame-retardant PBT/PC alloy, becomes charcoal and has certain compatibilization with polysiloxane/acrylate quasi-graft copolymer, novolac epoxy increase.Inorganic metal flame retardant of magnesium hydroxide decomposition temperature is higher, caloric receptivity is big, the magnesium oxide that decomposes generation is attached to the combustiblematerials surface and further stops incendiary to carry out, but also can absorb obnoxious flavour, smog and the imperfect combustion fusing residue that polymer burnings such as rubber, plastics are produced in a large number, burning is stopped very soon, in whole fire-retardant process, do not produce objectionable impurities, possess effects such as the contraction flexibility of filling the improvement system, heat-drawn wire simultaneously.The trade mark that Fushan City, Guangdong Province gold dagger-axe fire-fighting quipment company limited produces is to have formed the macromolecule layer with lubricating function and catalysis carbon-forming in the magnesium hydroxide surface of FM70D, FM70A and the microvoid, most of particle diameter is in 2～3 microns, particle size distribution 0.5～10 μ m, gradient is reasonable, in alloy substrate, be easy to disperse, all can form the good interface active layer with PBT, PC.Forming closely when containing the phosphoric acid ester oligopolymer of ignition-proof element phosphorus and magnesium hydroxide by burning, the charcoal layer has fire-retardant synergistic effect, and the phosphoric acid ester oligopolymer also has certain infiltration plastification to magnesium hydroxide, the processing fluidity difference situation of improvement system because of using inorganic powder activation magnesium hydroxide to cause, can also suppress transesterification reaction between PBT, the PC, reduce the substrate performance that causes by the hand transesterification reaction and descend.During the burning of polysiloxane in the polysiloxane/acrylate quasi-graft copolymer with the matrix siliceous firm charcoal layer of formation that interacts, charring rate height during the novolac epoxy burning, the two makes system become charcoal to increase considerably after adding, charcoal layer structure improved, iris action is strengthened, and the polysiloxane/acrylate quasi-graft copolymer has the esters of acrylic acid group, contain epoxide group on the novolac epoxy molecular structure, two class group and PBT, PC, all there is chemical interaction in the activation magnesium hydroxide, has certain increase-volume, the chain extension effect, make each component of system form an organic whole, flame retardant resistance is strong, mechanical property, thermal characteristics is good.
Compared with the prior art, the present invention has following beneficial effect:
(1) realized the halogen-free environment-friendly flame-proof of PBT/PC alloy, adopt 23%～33% activation magnesium hydroxide, and being aided with phosphoric acid ester oligopolymer fire retarding synergist, polysiloxane/acrylate quasi-graft copolymer, novolac epoxy char-forming agent make PBT/PC alloy vertical combustion reach the UL94V-0 level fully.
(2) PBT/PC alloy composite and corresponding PBT/PC alloy phase reduces more than 30% than thermal linear expansion coefficient, and heat-drawn wire increases more than 40 ℃, and the anti-contraction of material flexibility, heat-resistant stability are strengthened.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the scope that embodiment puts down in writing.
The polysiloxane/acrylate quasi-graft copolymer preparation method that following embodiment uses is referring to the preparation of application number 200710032309.9 disclosed flame-retardant interfacial modifiers.Typical preparation method is: prestox tetrasiloxane (D4) and phenyltrimethoxysila,e (PTMS) are joined in the Witco 1298 Soft Acid aqueous solution, and 50 ℃ were reacted 8 hours down, obtain the organic polysilsesquioxane emulsion of high phenyl; With sodium hydroxide solution the pH value is transferred to 10, add Sodium dodecylbenzene sulfonate, Potassium Persulphate and butyl acrylate then, reacted 6 hours down at 90 ℃; Add Sodium dodecylbenzene sulfonate, Potassium Persulphate and methyl methacrylate again, 90 ℃ were reacted 8 hours down, obtain the organic polysilsesquioxane of high phenyl/acrylate mixture emulsion, mass percent 10% calcium chloride water that adds 2 times of this quality of the emulsion, 95 ℃ of following heating demulsification types 10 hours, with precipitated product cleaning, drying, obtain the organic polysilsesquioxane/acrylate graft copolymers of high phenyl (Si-ACR) flame-retardant interfacial modifier; Wherein D4 is 1: 4 with the ratio of PTMS mole; Methyl methacrylate is 1: 1 with the ratio of butyl acrylate mole, organic polysilsesquioxane of high phenyl and polyacrylic ester mol ratio (R in graft copolymer
Si/ester) be 0.8～2: 1.
Condensation under acid catalyst forms employed novolac epoxy by pf resin of low molecular weight and epoxy chloropropane, has the advantage of resol and bisphenol A type epoxy resin concurrently.It is different with hydroxy radical content to press the lacquer resins molecular weight, can synthesize the novolac epoxy of different molecular weight and epoxy functionalities, and the present invention selects that epoxy functionalities is 3.0～5.0 for use, the novolac epoxy of high viscosity semisolid or solid state.
The activation magnesium hydroxide is for to carry out the surface-treated magnesium hydroxide with silane coupling agent, titanate coupling agent, stearic acid or stearate, and particle diameter is 0.5～10 μ m.This activation magnesium hydroxide activates magnesium hydroxide with FM70D, the FM70A of Fushan City, Guangdong Province gold dagger-axe fire-fighting quipment company limited.
As independent use FM70D, FM70A board activation magnesium hydroxide flame retardant PBT/PC alloy, mass percent is more than 50% in prescription for magnesium hydroxide, and the vertical combustion grade can reach UL94V-0@3.2mm, but because addition is big, the system mechanical property is relatively poor; Mass percent is that 45% activation magnesium hydroxide and the compound PBT/PC of the making alloy of 5% phosphoric acid ester oligopolymer reach same flame retardant rating in the employing prescription, and mechanical property increases on the basis of using the activation magnesium hydroxide flame retardant separately, but shock strength still remains on lower level; Use the polysiloxane/acrylate quasi-graft copolymer and the novolac epoxy of about 10% left and right sides mass percent can make activation magnesium hydroxide consumption reduce to 23～33%, the performance of each side is greatly improved.
Embodiment 1:
With 416g PBT, 176g PC, 240g FM70D, 50g R
Si/esterBe 0.8 Si-ACR, 60g RDP, 50g epoxy functionalities be 3.0 novolac epoxy, 4g dioctyl phthalate (DOP) softening agent, 2g Hinered phenols antioxidant 1010,2g silicone release after the high-speed mixer dispersing and mixing, by the dual-screw-stem machine fusion, mixing, extrude, cool off, dry, pelletizing and packing.Each subregion temperature of used double-screw extruding machine barrel is at 230～260 ℃.Prepared composition is injection molded into the standard batten of testing usefulness by standard size, and physicals is tested by international standard respectively.
Prepare material embodiment 1 of the present invention and other eight Example formulations such as table 1 to table 2 according to last noodle producing method.
As can be seen, all embodiment UL-94 vertical combustions are all by V-0 level (3.2mm) from table 1, table 2.Flame-retardant system magnesium hydroxide of the present invention and the fire-retardant synergistic of phosphoric acid ester oligopolymer, filling plasticising complementation, processing flowability is good.Two kinds of char-forming agents that adopted have esters of acrylic acid group and epoxide group respectively, two class groups exist increase-volume, chain extension effect with PBT, PC, activation magnesium hydroxide, make each component of system form indispensable organic whole, under lower magnesium hydroxide consumption, obtained higher flame retardant properties, and the system mechanical property is except that elongation at break is lower than the PBT/PC alloy, other performance all is higher than the PBT/PC alloy, and heat-drawn wire increases more than 40 ℃, and the anti-flexibility of shrinking of material obviously strengthens.
Table 1 Example formulations table and material property detected result
| Performance | Contrast | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PBT(g) | 696 | 416 | 474 | 430 | 400 |
| PC(g) | 296 | 176 | 118 | 154 | 140 |
| Si-ACR(g) | 0 | 50 (R Si/ester＝0.8) | 30(R Si/ester＝2) | 50(R Si/ester＝1.5) | 70(R Si/ester＝1.2) |
| Novolac epoxy (g) | 0 | 50 (n＝3.0) | 70(n＝3.5) | 60(n＝4.0) | 30 (n＝4.5) |
| Activation magnesium hydroxide (g) | 0 | 240 (FM70D) | 250(FM70A) | 240(FM70D) | 300 (FM70A) |
| Phosphoric acid ester oligopolymer (g) | 0 | 60 (RDP) | 50(RDP) | 60(BDP) | 50 (BDP) |
| Softening agent (g) | 4 (dioctyl phthalate (DOP)s) | 4 (dioctyl phthalate (DOP)s) | 4 (Zinic stearass) | 2 (Magnesium Stearates) | 4 (calcium stearates) |
| Oxidation inhibitor (g) | 2 (B215) | 2 (Hinered phenols antioxidants 1010) | 2 (phosphite antioxidants 168) | 2(B215) | 3 (B215) |
| Performance | Contrast | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Other (g) | 2 (silicone releases) | 2 (silicone releases) | 2 (photostabilizer GW-540) | 2 (photostabilizer Chimassorb119) | 3 (photostabilizer Chimassorb 2020) |
| Izod notched Izod impact strength (kJ/m 2) | 5.3 | 6.1 | 5.7 | 6.6 | 5.5 |
| Tensile strength (MPa) | 63 | 65 | 67 | 60 | 65 |
| Flexural strength (MPa) | 87 | 90 | 85 | 92 | 93 |
| Elongation at break (%) | 60 | 30 | 28 | 24 | 23 |
| Heat-drawn wire (℃, 0.45MPa) | 81 | 119 | 122 | 124 | 140 |
| Thermal linear expansion coefficient (* 10 5cm/cm.℃) | 8.7 | 5.4 | 5.3 | 5.5 | 5.1 |
| UL94 vertical combustion grade (3.2mm) | NR | V-0 | V-0 | V-0 | V-0 |
Table 2 Example formulations table and material property detected result
| Performance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| PBT(g) | 400 | 432 | 400 | 500 | 400 |
| PC(g) | 113 | 100 | 139 | 100 | 200 |
| Si-ACR(g) | 70(R Si/ester＝1) | 60(R Si/ester＝1.5) | 70(R Si/ester＝1.8) | 51 (R Si/ester＝2) | 50(R Si/ester＝0.8) |
| Novolac epoxy (g) | 30(n＝5.0) | 50 (n＝3.3) | 50 (n＝4.2) | 40 (n＝4.6) | 44 (n＝4.0) |
| Activation magnesium hydroxide (g) | 330(FM70D) | 280 (FM70A) | 300 (FM70D) | 240 (FM70A) | 230 (FM70D) |
| Phosphoric acid ester oligopolymer (g) | 50(RDP) | 70 (BDP) | 30 (BDP) | 60 (BDP) | 70 (RDP) |
| Softening agent (g) | 3 (polyethylene waxs) | 4 (Zinic stearass) | 5 (Magnesium Stearates) | 4 (calcium stearates) | 2 (dioctyl phthalate (DOP)s) |
| Oxidation inhibitor (g) | 2(B215) | 4 (Hinered phenols antioxidants 1010) | 3 (B215) | 2 (B215) | 2 (phosphite antioxidants 168) |
| Performance | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Other (g) | 2 (photostabilizer Chimassorb2020) | 0 | 3 (silicone releases) | 3 (photostabilizer GW-540) | 2 (silicone releases) |
| Izod notched Izod impact strength (kJ/m 2) | 5.6 | 6.2 | 6.7 | 5.9 | 7.2 |
| Tensile strength (MPa) | 78 | 72 | 75 | 77 | 72 |
| Flexural strength (MPa) | 93 | 92 | 91 | 87 | 85 |
| Elongation at break (%) | 23 | 27 | 28 | 28 | 20 |
| Heat-drawn wire (℃, 0.45MPa) | 146 | 134 | 142 | 123 | 146 |
| Thermal linear expansion coefficient (* 10 5cm/cm.℃) | 4.9 | 5.1 | 5.0 | 5.4 | 5.7 |
| UL94 vertical combustion grade (3.2mm) | V-0 | V-0 | V-0 | V-0 | V-0 |
Claims (8)
1. fire retardant PBT with no halogen/PC alloy composite, it is characterized in that, by mass percentage, its prescription is made up of following component: 40%～50%PBT, 10%～20%PC, 23%～33% activation magnesium hydroxide, 3%～7% phosphoric acid ester oligopolymer, 3%～7% polysiloxane/acrylate quasi-graft copolymer, 3%～7% novolac epoxy, 0.2%～0.4% oxidation inhibitor and 0.4%～0.8% processing aid.
2. fire retardant PBT with no halogen according to claim 1/PC alloy composite, it is characterized in that, described activation magnesium hydroxide is for to carry out the surface-treated magnesium hydroxide with silane coupling agent, titanate coupling agent, stearic acid or stearate, and particle diameter is 0.5～10 μ m.
3. fire retardant PBT with no halogen according to claim 1/PC alloy composite is characterized in that, described phosphoric acid ester oligopolymer is Resorcinol biphosphonate or low poly bisphenol two (diphenyl phosphoester).
4. fire retardant PBT with no halogen according to claim 1/PC alloy composite, it is characterized in that, described polysiloxane/acrylate quasi-graft copolymer is the organic polysilsesquioxane/acrylate graft copolymers of high phenyl, and organic polysilsesquioxane of high phenyl and polyacrylic ester mol ratio in graft copolymer is 0.8～2: 1.
5. fire retardant PBT with no halogen according to claim 1/PC alloy composite is characterized in that, the epoxy functionalities of described novolac epoxy is 3.0～5.0.
6. fire retardant PBT with no halogen according to claim 1/PC alloy composite is characterized in that, described oxidation inhibitor is phenolic antioxidant and/or phosphite ester kind antioxidant.
7. fire retardant PBT with no halogen according to claim 1/PC alloy composite is characterized in that, described processing aid is one or more in softening agent, releasing agent, photostabilizer, pigment and the dyestuff.
8. the preparation method of the described fire retardant PBT with no halogen of claim 1/PC alloy composite, it is characterized in that: press prescription quality per-cent, after PBT, PC, activation magnesium hydroxide, polysiloxane/acrylate quasi-graft copolymer, phosphoric acid ester oligopolymer, novolac epoxy, oxidation inhibitor and other processing aid dispersing and mixing, by the dual-screw-stem machine fusion, mixing, extrude, cool off, dry, pelletizing and packing, each subregion temperature of used double-screw extruding machine barrel remains on 230～260 ℃;
By mass percentage, fire retardant PBT with no halogen/PC alloy combination composition formula is made up of following component: 40%～50%PBT, 10%～20%PC, 23%～33% activation magnesium hydroxide, 3%～7% phosphoric acid ester oligopolymer, 3%～7% polysiloxane/acrylate quasi-graft copolymer, 3%～7% novolac epoxy, 0.2%～0.4% oxidation inhibitor and 0.4%～0.8% processing aid.
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