CN105315603A - Flame-retardant thermoplastic elastomer composition - Google Patents
Flame-retardant thermoplastic elastomer composition Download PDFInfo
- Publication number
- CN105315603A CN105315603A CN201510705141.8A CN201510705141A CN105315603A CN 105315603 A CN105315603 A CN 105315603A CN 201510705141 A CN201510705141 A CN 201510705141A CN 105315603 A CN105315603 A CN 105315603A
- Authority
- CN
- China
- Prior art keywords
- flame
- thermoplastic elastomer
- dioxide
- silicon
- elastomer composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract 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 title claims abstract description 33
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 64
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 62
- 239000003921 oil Substances 0.000 claims abstract description 31
- -1 poly triazinyl benzimidazole Chemical compound 0.000 claims abstract description 27
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229960001866 silicon dioxide Drugs 0.000 claims description 61
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229940064734 aminobenzoate Drugs 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 19
- 238000013329 compounding Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000000178 monomer Substances 0.000 description 38
- 239000007787 solid Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- 239000004743 Polypropylene Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 125000004306 triazinyl group Chemical group 0.000 description 10
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 9
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000012047 saturated solution Substances 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 9
- 239000012279 sodium borohydride Substances 0.000 description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- CWMYWRMDANXCSB-UHFFFAOYSA-N 1-oxoethanesulfonic acid Chemical compound CC(=O)S(O)(=O)=O CWMYWRMDANXCSB-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 239000008346 aqueous phase Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
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- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- LHQWDZSUXOBDOJ-UHFFFAOYSA-N calcium;cyanamide Chemical compound [Ca].NC#N LHQWDZSUXOBDOJ-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
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- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant thermoplastic elastomer composition. Preparation raw materials of the flame-retardant thermoplastic elastomer composition comprise 100 parts by weight of sulfonated SEBS, 50-60 parts by weight of MAH-g-PP, 10-30 parts by weight of white oil and 5-15 parts by weight of a flame retardant, wherein the flame retardant is prepared by compounding graphene-like silicon dioxide and hyperbranched poly triazinyl benzimidazole.
Description
Technical field
The present invention relates to a kind of thermoplastic elastomer, particularly
a kind of flame-retardant thermoplastic elastomer composition.
Background technology
Thermoplastic elastomer TPE(ThermoplasticElastomer) be a kind of snappiness, high strength, high resilience with rubber, having again can the material of injection molding feature, can recycle and reduce costs, both can secondary injection molding, with body material coating and bondings such as PP, PE, PC, PS, ABS, also can be shaping separately.But the combustibility of TPE limits it and further applies, and the application in some field even also can bring very large potential safety hazard, thus prepare the important research direction that high-performance refractory goods become its Application Areas.In prior art, generally inorganic combustion inhibitor is added in TPE material to prepare the material of high flame retardant grade.But the problem of the particle diameter of inorganics, consumption and consistency usually cause Flame Retardancy can with the serious unbalance of physical and mechanical properties, therefore mechanical property is as on the low side in tensile strength, elongation at break mostly, the while that processing characteristics being not good, the hardness of material is higher, and feel is not good.
Therefore, be starved of the improvement by formula and production technique, develop a kind of halogen-free flame-retardant thermoplastic elastomer simultaneously possessing high strength and high flame resistance.
Summary of the invention
In order to solve the problem, one aspect of the invention provides
a kind of flame-retardant thermoplastic elastomer composition, it is characterized in that, by weight, comprise:
The sulfonated SEBS of 100 weight parts;
The MAH-g-PP of 50-60 weight part;
The white oil of 10-30 weight part; With
The fire retardant of 5-15 weight part;
Wherein, described fire retardant is that class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound and prepare;
The structure of described poly-triazinyl benzoglyoxaline is such as formula [1], and described [1] structure is:
Wherein, R
1for the one in carboxyl, hydroxyl, amino, sulfonic group;
Described symbol " " for having the repeating unit of formula [1] representation,
As a kind of embodiment, the loading capacity of described sulfonated SEBS is 0.4-1.5.
As a kind of embodiment, the percentage of grafting of described MAH-g-PP is 1.5%-4.5%.
Described poly-triazinyl phenyl ring is by the bromo-1H-benzimidizole derivatives of 4,7-bis-and 1,3, the reaction of 5-tri-boronate s-triazine obtains, and described 4,7-bis-bromo-1H-benzimidizole derivatives and 1, the mol ratio of 3,5-tri-boronate s-triazine is 1:(1.1-2.2).
The compound of described class graphene-like silicon-dioxide and hyperbranched poly triazinyl phenyl ring is by class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine compound, then is obtained by reacting with the bromo-1H-benzimidizole derivatives of 4,7-bis-.
Described class graphene-like silicon-dioxide is by comprising graphene oxide, DMF, 3-(iso-butylene acyl-oxygen) raw material of propyl trimethoxy silicane and Diisopropyl azodicarboxylate prepares.
The mol ratio of described class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine is 1:(5-20).
The mol ratio of described class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine is 1:(10-15).
Described raw materials also comprises the additive of 0.1-5 weight part: one or more in talcum, calcium carbonate, wood powder, cellulose powder, weathering stabilizers, benzotriazole system UV absorption agent, thermo-stabilizer, aminobenzoate type photostabilizer, static inhibitor, aluminate, lubricant, silicone compounds.
The present invention another aspect provides described in preparation
a kind of flame-retardant thermoplastic elastomer compositionmethod, it is characterized in that,
(1) by described raw material, by weight after mixing, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 60-80 DEG C of hot air type hopper inner drying 2-4 hour;
(3) by the product of step (2) gained, in 170 DEG C of-220 DEG C of vacuum injections in mould, and under vacuum, this temperature 0.5-20 hour is kept, then cooling curing, obtain flame-retardant thermoplastic elastomer.
Embodiment
The detailed description of the following preferred implementation method of the present invention of participation in the election and the embodiment comprised can more easily understand content of the present invention.Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be as the criterion with the definition in this specification sheets.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope is single
only public affairsopen.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope meaning
figurecomprise its end value and all integers within the scope of this and mark.
Singulative comprises plural number and object is discussed, unless clearly indicated in addition in context." optional " or " any one " refer to that the item that describes thereafter or event can occur or not occur, and this description comprises situation that event occurs and the situation that event does not occur.
Approximate term in specification sheets and claims is used for modifying quantity, represents that the present invention is not limited to this concrete quantity, also comprises close to this quantity acceptable and can not cause the part of the correction of the change of relevant basic function.Accordingly, modify a numerical value with " approximately ", " about " etc., mean and the invention is not restricted to this exact numerical.In some example, approximate term may correspond to the precision of the instrument measuring numerical value.In present specification and claims, scope limits and can combine and/or exchange, if do not illustrate that these scopes comprise contained all subranges therebetween in addition.
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
" polymkeric substance " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.Generic term " polymkeric substance " comprises term " homopolymer ", " multipolymer ", " terpolymer " and " interpolymer ".
" interpolymer " means the polymkeric substance prepared by polymerization at least two kinds of different monomers.Generic term " interpolymer " comprises term " multipolymer " (it is generally in order to refer to the polymkeric substance prepared by two kinds of different monomers) and term " terpolymer " (it is generally in order to refer to the polymkeric substance prepared by three kinds of different monomers).It also comprises plants monomer and the polymkeric substance that manufactures by being polymerized four or more." blend " mean two or more polymkeric substance by physics or the side of chemistry
method altogetherthe polymkeric substance formed with mixing.
One aspect of the invention provides
a kind of flame-retardant thermoplastic elastomer composition, it is characterized in that, by weight, comprise:
The sulfonated SEBS of 100 weight parts;
The MAH-g-PP of 50-60 weight part;
The white oil of 10-30 weight part;
The fire retardant of 5-15 weight part; With
Wherein, described fire retardant is that class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound and prepare;
The structure of described poly-triazinyl phenyl ring is such as formula [1], and described formula [1] structure is:
Wherein, R
1for the one in carboxyl, hydroxyl, amino, sulfonic group;
Described symbol " " for having the repeating unit of formula [1] representation,
As a kind of embodiment, the loading capacity of described sulfonated SEBS is 0.4-1.5.
As a kind of embodiment, the percentage of grafting of described MAH-g-PP is 1.5%-4.5%.
Described poly-triazinyl phenyl ring is by the bromo-1H-benzimidizole derivatives of 4,7-bis-and 1,3, the reaction of 5-tri-boronate s-triazine obtains, and described 4,7-bis-bromo-1H-benzimidizole derivatives and 1, the mol ratio of 3,5-tri-boronate s-triazine is 1:(1.1-2.2).
The compound of described class graphene-like silicon-dioxide and hyperbranched poly triazinyl phenyl ring is by class graphene-like silicon-dioxide and the reaction of 1,3,5-tri-boronate s-triazine, then is obtained by reacting with the bromo-1H-benzimidizole derivatives of 4,7-bis-.
Described class graphene-like silicon-dioxide is by comprising graphene oxide, DMF, 3-(iso-butylene acyl-oxygen) raw material of propyl trimethoxy silicane and Diisopropyl azodicarboxylate prepares.
The mol ratio of described class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine is 1:(5-20).
The mol ratio of described class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine is 1:(10-15).
Described raw materials also comprises the additive of 0.1-5 weight part; Described additive comprise in aluminium hydroxide, magnesium hydroxide, calcium aluminate, triphenylphosphate, Tritolyl Phosphate, phosphoric acid dihydroxyphenyl propane-bis-diphenyl ester and phosphoric acid Resorcinol-bis-diphenyl ester, ammonium polyphosphate, polyphosphoric acid melamine, polyphosphoric acid piperazine, ortho-phosphoric acid piperazine, melamine pyrophosphate, piperazine pyrophosphate, polyphosphoric acid melamine, ortho-phosphoric acid trimeric cyanamide, calcium phosphate and trimagnesium phosphate one or more.
The present invention another aspect provides described in preparation
a kind of flame-retardant thermoplastic elastomer compositionmethod, it is characterized in that,
(1) by described raw material, by weight after mixing, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 60-80 DEG C of hot air type hopper inner drying 2-4 hour;
(3) by the product of step (2) gained, in 170 DEG C of-220 DEG C of vacuum injections in mould, and under vacuum, this temperature 0.5-20 hour is kept, then cooling curing, obtain flame-retardant thermoplastic elastomer.
sulfonated SEBS:
The term " sulfonated SEBS " used in the application refers to and carries out sulfonation process to SEBS; it is made to possess certain sulfonation degree; the vitriol oil, oleum or acetyl sulfonate such as can be used as sulfonated reagent, and preferably, sulfonated SEBS can adopt following methods to prepare:
(1) under the condition of ice bath; 100ml1 is added in three-necked bottle; 2-ethylene dichloride (DEC); then add the diacetyl oxide of 0.1mol, at the uniform velocity stir, time below its temperature equilibrium to 5 DEG C; be added dropwise to the vitriol oil of 0.11mol; withdrawn ice bath after reaction 30min, rapid stirring 10min under room temperature, namely obtains fresh acetyl sulfonate.
(2) 5gSEBS is added be equipped with in the there-necked flask of 160mLDCE; fill nitrogen; 45 DEG C of water-baths; electric stirring; backflow, the hexanaphthene then adding 20mL makes it fully dissolve, until solution is transparent; the acetyl sulfonate 5-30mL adding fresh preparation subsequently carries out sulfonation reaction as sulphonating agent, adds 50mL Virahol stopped reaction after reaction 5h.
(3) mix products 40 DEG C of underpressure distillation go out mixed solvent, obtain viscous solid product, pour out after utilizing aqueous phase transfer method to precipitate, 90 DEG C are boiled a few hours subsequently, until a small amount of solvent evaporates is to the greatest extent, cools, wash and suction filtration, until filtrate is neutral, filter residue is fully dry at 40 DEG C in a vacuum, obtains.
In above-mentioned preparation method, by controlling the consumption of acetyl sulfonate, effectively can control the sulfonation degree of sulfonated SEBS, such as consumption is 10mL and 23mL, and the loading capacity of sulfonated SEBS reclaimed materials is respectively 0.4 and 1.5.
In one embodiment, the loading capacity of described sulfonated SEBS is 0.4-1.5; Preferably, the loading capacity of described sulfonated SEBS is 0.8-1.4; More preferably, the loading capacity of described sulfonated SEBS is 1.0-1.3; Most preferably, the loading capacity of described sulfonated SEBS is 1.2.
Term " loading capacity " in the application refers in 1 gram of sulfonated SEBS, the mmole number of sulfonic acid group.
MAH-g-PP：
In this specification sheets, term " MAH-g-PP " refers to maleic anhydride (MAH) graft modification polypropylene (PP), and the MAH-g-PP as raw material of the present invention is not particularly limited, and can be commercially available acquisition, also can pass through solution method, supercritical CO
2the method synthesis well-known to those skilled in the art such as solution method, scorification, radiation method and solid phase method obtains.Wherein, when solution method carries out PP grafting MAH, the graft reaction time is long, and grafting efficiency is low, needs to consume poisonous, flammable solvent in a large number, and production cost is high, large to human injury, contaminate environment, takes up an area large, is difficult to realize continuous operation.Therefore, preferably scorification is adopted.
Such as, prepare MAH-g-PP with scorification: by vinylbenzene and the mixing of initiator dicumyl peroxide, dissolve, be made into the styrene solution of initiator.Polypropylene and maleic anhydride are mixed into mixture, the mixture of polypropylene and maleic anhydride is inputted twin screw extruder, after its melting, by the different barrel section continuous measurement inputs of the styrene solution of initiator at twin screw extruder, carry out melting graft reaction, obtain MAH-g-PP.
In described MAH-g-PP, MAH percentage of grafting is 1.5%-4.5%; Preferably, the percentage of grafting of MAH is 2.3%-4.0%, and further preferably, the percentage of grafting of MAH is 3.5%.
In the present invention, in embodiment and comparative example, MAH percentage of grafting adopts acid base titration test.
The main process of acid base titration: take 0.5g polypropylene grafted maleic anhydride and be dissolved in the hot dimethylbenzene of 50mL, the NaOH-ethanolic soln of 10mL0.1mol/L is added until completely dissolved in system, reflux 10 minutes, anhydride group in maleic anhydride and alkali are fully reacted, after add while hot trace deionized water (50 μ l) or pyridine/DMF in system, promote anhydride hydrolyzes become carboxylic acid.Add 3 phenolphthalein indicators, rear hydrochloric acid/Virahol is titrated to terminal simultaneously.If HCl/ aqueous isopropanol concentration is C (mol/L), titration M (g) sample, consume volume V1 (mL) solution, blank titration consumes V2 (mL), and percentage of grafting G is calculated as follows:
G=C(V2-V1)×98/（2×M×1000）×100%
In formula, 98 is MAH molecular weight.
MAH-g-PP described in the present invention also can be commercially available.
white oil:
White oil is by the mixture of oil gained refining liquid hydrocarbon, is mainly saturated naphthenic hydrocarbon and alkane mixture, and crude oil is through normal pressure and vacuum fractionation, solvent extraction and dewaxing, hydrofining and obtaining.White oil, mainly as lubricant, improves two-phase consistency.
The application is not particularly limited white oil, can commercially availablely obtain.Preferably, the white oil of conformance with standard Q/MSH32-2009.
class graphene-like silicon-dioxide:
In the present invention, described term " class graphene-like silicon-dioxide " is for having the silicon-dioxide of similar graphene platelet shape.
As a kind of embodiment, the graphene-like of class described in the present invention silicon-dioxide can be prepared by following methods: appropriate graphene oxide is dissolved in N, in dinethylformamide, add appropriate 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane monomer again, then logical nitrogen, under agitation adds initiator; At 65 DEG C after water-bath 36h, centrifugal, dry, thermal treatment 10h at product being placed in 700 DEG C, obtains class graphene-like silicon-dioxide.
In the present invention, described graphene oxide is the product of powdered graphite after chemical oxidation and stripping, and graphene oxide is single atomic shell, can expand to some tens of pm at any time on lateral dimension, therefore, its construct trans typical size of general chemistry and Materials science.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, has polymkeric substance, colloid, film, and amphiphilic characteristic.After oxide treatment, graphite oxide still keeps the laminate structure of graphite, but on the Graphene monolithic of every one deck, introduce many oxygen base functional groups.Graphene oxide is generally oxidized through strong acid by graphite and obtains.Mainly contain the method that three kinds are prepared graphite oxide: Brodie method, Staudenmaier method and Hummers method.Wherein Hummers method preparation process ageing relatively better and also safer in preparation process, be one the most frequently used at present.Potassium permanganate in its employing vitriol oil and powdered graphite are after oxidizing reaction, obtain the brown graphite flake having derivative carboxylic acid group at edge and be mainly phenolic hydroxyl group and epoxide group in the plane, this graphene layers can be peeled off as graphene oxide through ultrasonic or high-shear vigorous stirring, and in water, form single-layer graphene oxide suspension that is stable, sundown.Because conjugate network is subject to serious functionalized, graphene oxide thin slice has the speciality of insulation.Can enter through reduction treatment
row portiondivide reduction, obtain the graphene platelet of chemically modified.At present, prepare graphene oxide novel method and emerged in an endless stream, be divided into top-down approach and the large class of Bottom-up approach two substantially.The former thinking splits crystalline flake graphite etc. to prepare graphene oxide, improves one's methods as representative with traditional three methods, also comprises method of fractionation (breaking) carbon nanotube etc.The latter is the method for synthesizing by various carbon source, and concrete grammar is multifarious, of a great variety.
In the present invention, the thickness of described class graphene-like silicon-dioxide is 1-5nm.
In the present invention, described class graphene-like silicon-dioxide is similar graphene oxide lamellar structure.
hyperbranched poly triazinyl phenyl ring:
The triazinyl of hyperbranched poly described in the present invention phenyl ring is obtained through Suzuki linked reaction by the bromo-1H-benzimidizole derivatives of 4,7-bis-and 1,3,5-tri-boronate s-triazine, as follows shown in reaction process:
Described symbol " " is for having the repeating unit of hyperbranched poly triazinyl phenyl ring.
In Suzuki reaction, through lot of experiment validation, using palladium complex as catalyzer, described palladium complex can be zeroth order palladium complex, such as, and tetrakis triphenylphosphine palladium.Also can be non-zero valence palladium complex, such as, palladium, palladium chloride, [1,1 '-bis-(diphenylphosphino) ferrocene] palladium chloride.
Described organic solvent can be the one in ethanol, Isosorbide-5-Nitrae-dioxane, DMF, toluene, tetrahydrofuran (THF).
Described alkali can be the one in hydrated barta, sodium carbonate, salt of wormwood, cesium carbonate, cesium fluoride, potassiumphosphate.
KOAc is optimal weak base catalyst, and stronger alkaline catalysts can make starting aryl halogen generation self-coupling reaction; In Suzuki reaction, good solvent is DMSO and DMF, can also select dioxane and tuluene; As the catalyzer of whole reaction, Pd (dppf) Cl
2generally can result preferably.
In described Suzuki reaction, the add-on excessive relative to halogenated aryl hydrocarbon 10% of described 1,3,5-tri-boronate triazine, this is because deboration can cause the loss of aryl boric acid; But, if 1,3,5-tri-boronate triazine is first converted into ester, be used further to linked reaction, the loss of reaction mesoboric acid can be reduced.
In the present invention, the mol ratio of described 4,7-bis-bromo-1H-benzimidizole derivatives and 1,3,5-tri-boronate s-triazine is 1:(1.1-2.2), be preferably 1:1.8.
The preparation of 1,3,5-tri-boronate triazine can be prepared by any one method well known by persons skilled in the art.
Such as:
Wherein, R is the one in methyl, ethyl, propyl group, butyl; X is Cl or Br, is preferably Br.
Described 1,3,5-tri-boronate s-triazine also can be commercially available.
The preparation of the bromo-1H-benzimidizole derivatives of 4,7-bis-can adopt following methods to prepare:
(1) by 5g2,1,3-diazosulfide is reflux in the solution of 15mlHBr, is stirring the Br simultaneously dripping 5.7ml
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
In the present invention, described 4,7-bis-bromo-1H-benzoglyoxalines also can be commercially available.
In the present invention, the sulfonic acid group in sulfonated SEBS both can with imidazole group generation ionomer, Fu Ke-acylation reaction can be there is with the phenyl ring of the electron rich in composition again, improve cross-linking density, because herein is provided Advantageous Effects of the present invention.
the compound of class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline:
In the present invention, the compound of described class graphene-like silicon-dioxide and hyperbranched poly triazinyl phenyl ring, first be class graphene-like silicon-dioxide and monomer 1, 3, 5-tri-boronate s-triazine reacts, i.e. grafted monomer 1 on the surface of class graphene-like silicon-dioxide, 3, 5-tri-boronate s-triazine, and then will with monomer 1, 3, the class graphene-like silicon dioxide of 5-tri-boronate s-triazine grafting joins 1, 3, 5-tri-boronate s-triazine and 1, in the Suzuki linked reaction of 4-phenyl-dihalide derivative, carry out further complex reaction, result can obtain the surface grafting poly-triazinyl phenyl ring of dissaving structure at class graphene-like silicon-dioxide.
In the present invention, the reaction of described class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine, can utilize the hydroxyl on the hydroxyl of class graphene-like silica sphere and monomer 1,3,5-tri-boronate s-triazine to react.Described reaction can adopt any one method well known by persons skilled in the art to prepare.Such as, monomer 1,3,5-tri-boronate s-triazine, little over amount, adds appropriate class graphene-like silicon-dioxide and the vitriol oil, reacting by heating, grafting a lot of monomer 1,3,5-tri-boronate s-triazine on the surface obtaining class graphene-like silicon-dioxide.
In the present invention, described class graphene-like silicon-dioxide and monomer 1,3, the reaction of 5-tri-boronate s-triazine, also can first process class graphene-like silica sphere, make its surface with the group that can react with boronate, such as hydroxyl, aldehyde radical etc., and then further react.
Polymer materials is the macromolecular organic compound containing a lot of carbon, protium, under the effect of certain temperature and oxygen, can cause violent ignition.Described combustion processes is, after polymer materials is heated, heat conduction enters material internal, and first material absorbs heat melting; Temperature continues to raise, and the key of some poor heat stability starts fracture, and the thermolysis of polymkeric substance starts and discharges inflammable gas, when inflammable gas reaches finite concentration and temperature, can react with oxygen, ignition occurs; The heat that burning produces can be fed back to undecomposed solid combustible again by gaseous combustion, aggravates melting and the decomposition of polymkeric substance further, produces more inflammable gas, burning is aggravated.
Described fire retardant joins after in the middle of TPE system, and when system is at heated combustion, described fire retardant can form one deck foam layer, and described foam layer can play heat insulation, oxygen barrier, press down the effect of cigarette, and prevents molten drop from producing.
Simultaneously, through a large amount of experiments, the present inventor finds unexpectedly, due to fire retardant have hyperbranched structure make the add-on of described fire retardant little time, just can play good flame retardant effect, simultaneously due to characteristic that silicon-dioxide itself is excellent, add the form of its class graphene-like outward, not only larger, more effectively can play flame retardant effect, improve thermostability, the mechanical property of system can be improved again simultaneously; Add outward on described dissaving structure containing a large amount of carboxyls; at high temperature and under the condition of vacuum hydro-extraction; can with the phenyl ring generation friedel-crafts acylation on styrene units in sulfonated SEBS, thus occur further crosslinked, improve the tensile strength of whole matrix material.
other:
Of the present invention
a kind of flame-retardant thermoplastic elastomer compositionin, suitably can coordinate weighting agent to use as required.As packing material, be not particularly limited, can be inorganic filler (such as, talcum, calcium carbonate and calcined kaolin), organic filler (such as, fiber, wood powder and cellulose powder), antioxidant (such as, phenol system, sulphur system, phosphorus system, the antioxidant of lactone system and prime system of supporting one's family), weathering stabilizers, UV absorption agent (such as, benzotriazole system, three diamines (tridiamine) are, N-anilide system and benzophenone series UV absorption agent), thermo-stabilizer, photostabilizer (such as, hindered amine as light stabilizer and aminobenzoate type photostabilizer), static inhibitor, nucleator, pigment, sorbent material (such as, metal oxide), metal chloride (such as, iron(ic) chloride and calcium chloride), hydrotalcite, aluminate, lubricant (such as, lipid acid, higher alcohols, aliphatic amides and aliphatic ester) and silicone compounds.
Another aspect provides described in preparation
a kind of flame-retardant thermoplastic elastomer compositionmethod, it is characterized in that,
(1) by described raw material, by weight after mixing, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 60-80 DEG C of hot air type hopper inner drying 2-4 hour;
(3) by the product of step (2) gained, in 170 DEG C of-220 DEG C of vacuum injections in mould, and under vacuum, this temperature 0.5-20 hour is kept, then cooling curing, obtain flame-retardant thermoplastic elastomer.
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, Jun Gou Chemical Reagent Co., Ltd., Sinopharm Group, and following material number used is weight part.
Raw material:
A1: sulfonated SEBS (loading capacity is 0.4)
A2: sulfonated SEBS (loading capacity is 1.2)
A3: sulfonated SEBS (loading capacity is 1.5)
A4:SEBS(non-sulfonated)
B1:MAH-g-PP(MAH percentage of grafting 1.5%)
B2:MAH-g-PP(MAH percentage of grafting 3.5%)
B3:MAH-g-PP(MAH percentage of grafting 4.5%)
C: fire retardant
Wherein, the mol ratio of class graphene-like silicon-dioxide and the positive triazine of 1,3,5-tri-boronate is designated as X
table 1
The preparation method of C1:
The synthetic route of the bromo-5-carboxyl of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by 5g5-carboxyl-2,1,3-diazosulfide reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 13 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C2:
The synthetic route of the bromo-5-carboxyl of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by 5g5-carboxyl-2,1,3-diazosulfide reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 17 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C3:
The synthetic route of the bromo-5-hydroxyl of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by 5g5-hydroxyl-2,1,3-diazosulfide reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 9 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C4:
The synthetic route of the bromo-5-hydroxyl of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by 5g5-hydroxyl-2,1,3-diazosulfide reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 10 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C5:
The synthetic route of the bromo-5-amino of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by amino-2,1, the 3-diazosulfide of 5g5-reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 5 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C6:
The synthetic route of the bromo-5-amino of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by amino-2,1, the 3-diazosulfide of 5g5-reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 15 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C7:
The synthetic route of the bromo-5-sulfonic group of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by 5g5-sulfonic group-2,1,3-diazosulfide reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 20 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
The preparation method of C8:
The synthetic route of the bromo-5-sulfonic group of [1] 4,7-bis--1H-benzoglyoxaline:
(1) by 5g5-sulfonic group-2,1,3-diazosulfide reflux in the solution of 15mlHBr, the Br simultaneously dripping 5.7ml is being stirred
230min; Mixture is refluxed 3 hours, be then cooled to room temperature, with the saturated solution of sodium bisulfite by unnecessary Br
2wash away, filter and obtain solid (1);
(2) product got in 3.5g solid (1) is dissolved in 400mlEtOH and 40mlTHF, under the condition of nitrogen, adds the sodium borohydride of 8.11g in batches, stirs 10 minutes at 0 DEG C, and then at room temperature stirs 3 hours; After removal of solvent under reduced pressure, by resistates 150mlEt
2o dilutes, and by salt water washing, dried over mgso, obtains solid (2);
(3) 2.11g solid (2) is dissolved in 70ml methylene dichloride, then adds the HC (OEt) of 1.06ml in the solution
3, stir 10 minutes, then add the camphorsulfonic acid of 20mg as catalyzer, react after 1 hour, filtration, washing, drying, obtain product.
Concrete reaction process is shown below:
[2] reaction of class graphene-like silicon-dioxide and monomer 1,3,5-tri-boronate s-triazine
By monomer 1,3, the 5-tri-boronate s-triazine of the class graphene-like silicon-dioxide of 1 weight part and 13 weight parts under the condition of the vitriol oil as catalyzer, reacting by heating, obtains product (2);
[3] class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound
To in one 50 milliliters three neck round-bottomed flasks, by product (2), monomer 1,3,5-tri-boronate s-triazine and the bromo-5-carboxyl of 4,7-bis--1H-benzoglyoxaline at KOAc as weak base catalyst, DMSO is solvent, Pd (dppf) Cl
2for under the condition of catalyzer, pass into nitrogen 30 minutes, then at 85 DEG C, oil bath heats 5 hours, then reaction mixture is cooled to room temperature, and dilutes with water, generates precipitation, then dilute with water dry, to obtain final product.
D: white oil
E: other
table 2specific embodiment
testing method
Above-described embodiment 1-15 is prepared into strip, and tests, testing method is as follows:
Tensile property: tensile strength and elongation at break measure according to JISK6251.
Flame retardant resistance: measure according to UL94 standard.
Test result is shown in
table 3.
table 3
Above data can be found out, compared with not using the product of sulfonated SEBS, fire retardant, material prepared by the present invention, while possessing high strength, also has good flame retardant resistance, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. a flame-retardant thermoplastic elastomer composition, is characterized in that, by weight, comprises:
The sulfonated SEBS of 100 weight parts;
The MAH-g-PP of 50-60 weight part;
The white oil of 10-30 weight part; With
The fire retardant of 5-15 weight part;
Wherein, described fire retardant is that class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline carry out compound and prepare;
The structure of described hyperbranched poly triazinyl benzoglyoxaline is such as formula [1], and described formula [1] structure is:
Wherein, R
1for the one in carboxyl, hydroxyl, amino, sulfonic group;
Described symbol " " is for having the repeating unit of formula [1] representation.
2. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, is characterized in that, the loading capacity of described sulfonated SEBS is 0.4-1.5.
3. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, is characterized in that, the percentage of grafting of described MAH-g-PP is 1.5%-4.5%.
4. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, it is characterized in that, described poly-triazinyl benzoglyoxaline is by 4, the bromo-1H-benzimidizole derivatives of 7-bis-and the reaction of 1,3,5-tri-boronate s-triazine obtain, and described 4, the mol ratio of the bromo-1H-benzimidizole derivatives of 7-bis-and 1,3,5-tri-boronate s-triazine is 1:(1.1-2.2).
5. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, it is characterized in that, the compound of described class graphene-like silicon-dioxide and hyperbranched poly triazinyl benzoglyoxaline is by class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine reacts, be obtained by reacting with 4,7-bis-bromo-1H-benzimidizole derivatives is hyperbranched again.
6. a kind of flame-retardant thermoplastic elastomer composition according to claim 5, it is characterized in that, described class graphene-like silicon-dioxide is by comprising graphene oxide, DMF, 3-(iso-butylene acyl-oxygen) raw material of propyl trimethoxy silicane and Diisopropyl azodicarboxylate prepares.
7. a kind of flame-retardant thermoplastic elastomer composition according to claim 5, is characterized in that, the mol ratio of described class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine is 1:(5-20).
8. a kind of flame-retardant thermoplastic elastomer composition according to claim 5, is characterized in that, the mol ratio of described class graphene-like silicon-dioxide and 1,3,5-tri-boronate s-triazine is 1:(10-15).
9. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, it is characterized in that, described composition also comprises the additive of 0.1-5 weight part: one or more in talcum, calcium carbonate, wood powder, cellulose powder, weathering stabilizers, benzotriazole system UV absorption agent, thermo-stabilizer, aminobenzoate type photostabilizer, static inhibitor, aluminate, lubricant, silicone compounds.
10. prepare an a kind of flame-retardant thermoplastic elastomer composition as claimed in claim 1, it is characterized in that,
(1) by the raw material described in claim any one of claim 1-9, by weight after mixing, through double-screw extruding pelletizing;
(2) product that step (1) obtains is placed on 60-80 DEG C of hot air type hopper inner drying 2-4 hour;
(3) by the product of step (2) gained, in 170 DEG C of-220 DEG C of vacuum injections in mould, and under vacuum, this temperature 0.5-20 hour is kept, then cooling curing, obtain flame-retardant thermoplastic elastomer.
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