CN105315603B - A kind of flame-retardant thermoplastic elastomer composition - Google Patents
A kind of flame-retardant thermoplastic elastomer composition Download PDFInfo
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- CN105315603B CN105315603B CN201510705141.8A CN201510705141A CN105315603B CN 105315603 B CN105315603 B CN 105315603B CN 201510705141 A CN201510705141 A CN 201510705141A CN 105315603 B CN105315603 B CN 105315603B
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- China
- Prior art keywords
- flame
- triazine
- thermoplastic elastomer
- silica
- weight
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000003063 flame retardant Substances 0.000 title claims abstract description 42
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 34
- 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 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 60
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 26
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- -1 bromo- boronate s-triazine Chemical compound 0.000 claims description 61
- 239000000047 product Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000003921 oil Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- 239000006227 byproduct Substances 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- 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
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
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- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 2
- 229940064734 aminobenzoate Drugs 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 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
- 239000003054 catalyst Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 239000004743 Polypropylene Substances 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000005406 washing Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- 235000019341 magnesium sulphate Nutrition 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 9
- 239000012279 sodium borohydride Substances 0.000 description 9
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 239000000376 reactant Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000012047 saturated solution Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- CWMYWRMDANXCSB-UHFFFAOYSA-N 1-oxoethanesulfonic acid Chemical compound CC(=O)S(O)(=O)=O CWMYWRMDANXCSB-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005516 engineering process 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
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 0 C**(*1)*c2c1c(*)ccc2* Chemical compound C**(*1)*c2c1c(*)ccc2* 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
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- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
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- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
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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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- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 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
- 150000002596 lactones Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 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
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 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
- 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
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 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
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 241000894007 species Species 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
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of flame-retardant thermoplastic elastomer composition, its preparing raw material include：The sulfonated SEBS of 100 parts by weight；The MAH g PP of 50 60 parts by weight；The white oil of 10 30 parts by weight；With the fire retardant of 5 15 parts by weight；Wherein, the fire retardant is that class graphene-like silica and hyperbranched poly triazine radical benzimidazole carry out compound be prepared.
Description
Technical field
The present invention relates to a kind of thermoplastic elastomer (TPE), more particularly to a kind of flame-retardant thermoplastic elastomer composition.
Background technology
Thermoplastic elastomer (TPE) TPE (Thermoplastic Elastomer) is a kind of high resiliency with rubber, high-strength
Degree, high resilience, again have can injection molding feature material, can recycle reduces cost, both can with quadric injection mould into
Type, can also be separately formed with the matrix material coating and bonding such as PP, PE, PC, PS, ABS.But TPE combustibility limits
Its further popularization and application, the application in some fields even can also bring very big potential safety hazard, thus prepare high-performance
Fire-retardant product turns into the important research direction of its application field.In the prior art, typically inorganic combustion inhibitor is added in TPE material
To prepare the material of high fire-retardance grade.But the problem of particle diameter of inorganic matter, dosage and compatibility, frequently results in Flame Retardancy
Can be with the serious unbalance of physical and mechanical properties, therefore mechanical performance such as tensile strength, elongation at break is relatively low mostly, processing characteristics
Bad while material hardness is higher, and feel is bad etc..
Hence it is highly desirable to by the improvement of formula and production technology, exploitation one kind is provided simultaneously with high intensity and height
The halogen-free flame-retardant thermoplastic elastomer of fire resistance.
The content of the invention
In order to solve the above problems, one aspect of the invention provides a kind of flame-retardant thermoplastic elastomer composition, and it is special
Sign is, by weight, comprising：
The sulfonated SEBS of 100 parts by weight；
The MAH-g-PP of 50-60 parts by weight；
The white oil of 10-30 parts by weight；With
The fire retardant of 5-15 parts by weight；
Wherein, the fire retardant is that class graphene-like silica and hyperbranched poly triazine radical benzimidazole carry out compound system
It is standby to obtain；
The structure such as formula [1] of the poly- triazine radical benzimidazole, [1] structure are：
Wherein, R1For one kind in carboxyl, hydroxyl, amino, sulfonic group；
The symbolFor the repeat unit with formula [1] representation,
As a kind of embodiment, the ion exchange capacity of the sulfonated SEBS is 0.4-1.5.
As a kind of embodiment, the grafting rate of the MAH-g-PP is 1.5%-4.5%.
The poly- triazine radical phenyl ring is anti-by the bromo- 1H- benzimidizole derivatives of 4,7- bis- and the boronate s-triazine of 2,4,6- tri-
It should obtain, and the bromo- 1H- benzimidizole derivatives of 4, the 7- bis- and 2, the mol ratio of 4,6- tri- boronate s-triazine is 1：
(1.1-2.2)。
The compound of class graphene-like silica and hyperbranched poly the triazine radical phenyl ring is by class graphene-like dioxy
SiClx and 2,4,6- tri- boronate s-triazine are compound, then react to obtain with the bromo- 1H- benzimidizole derivatives of 4,7- bis-.
The class graphene-like silica is by including graphene oxide, N,N-dimethylformamide, 3- (methacryloyls
Oxygen) raw material of propyl trimethoxy silicane and azodiisobutyronitrile is prepared.
The class graphene-like silica and 1, the mol ratio of 3,5- tri- boronate s-triazine is 1：(5-20).
The class graphene-like silica and 1, the mol ratio of 3,5- tri- boronate s-triazine is 1：(10-15).
The preparing raw material also includes the additive of 0.1-5 parts by weight：It is talcum, calcium carbonate, wood powder, cellulose powder, resistance to
Wait stabilizer, enumerate BTA system UV absorbents, heat stabilizer, aminobenzoate type light stabilizer, antistatic additive, aluminate, lubrication
One or more in agent, silicone compounds.
Another aspect of the invention provides the method for preparing a kind of flame-retardant thermoplastic elastomer composition,
(1) by described raw material, after mixing by weight, through double-screw extruding pelletizing；
(2) product that step (1) obtains is placed in 60-80 DEG C of hot air type hopper and dries 2-4 hours；
(3) by step (2) obtained by product, in 170 DEG C of -220 DEG C of vacuum injections into mould, and under vacuum,
Kept for temperature 0.5-20 hours, then cooled and solidified, obtain flame-retardant thermoplastic elastomer.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this
Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer prepared by polymerizeing at least two different monomers.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (its typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization for planting monomer by polymerization four or more to manufacture
Thing." blend " means that two or more polymer mixes the polymerization to be formed by physics or chemical method jointly
Thing.
One aspect of the invention provides a kind of flame-retardant thermoplastic elastomer composition, it is characterised in that by weight,
Comprising：
The sulfonated SEBS of 100 parts by weight；
The MAH-g-PP of 50-60 parts by weight；
The white oil of 10-30 parts by weight；
The fire retardant of 5-15 parts by weight；With
Wherein, the fire retardant is that class graphene-like silica and hyperbranched poly triazine radical benzimidazole carry out compound system
It is standby to obtain；
The structure such as formula [1] of the poly- triazine radical phenyl ring, formula [1] structure are：
Wherein, R1For one kind in carboxyl, hydroxyl, amino, sulfonic group；
The symbolFor the repeat unit with formula [1] representation,
As a kind of embodiment, the ion exchange capacity of the sulfonated SEBS is 0.4-1.5.
As a kind of embodiment, the grafting rate of the MAH-g-PP is 1.5%-4.5%.
The poly- triazine radical phenyl ring is anti-by the bromo- 1H- benzimidizole derivatives of 4,7- bis- and the boronate s-triazine of 2,4,6- tri-
It should obtain, and the bromo- 1H- benzimidizole derivatives of 4, the 7- bis- and 2, the mol ratio of 4,6- tri- boronate s-triazine is 1：
(1.1-2.2)。
The compound of class graphene-like silica and hyperbranched poly the triazine radical phenyl ring is by class graphene-like dioxy
SiClx and 2, the reaction of 4,6- tri- boronate s-triazine, then react to obtain with the bromo- 1H- benzimidizole derivatives of 4,7- bis-.
The class graphene-like silica is by including graphene oxide, N,N-dimethylformamide, 3- (methacryloyls
Oxygen) raw material of propyl trimethoxy silicane and azodiisobutyronitrile is prepared.
The mol ratio of the boronate s-triazine of class graphene-like silica and 2,4,6- tri- is 1：(5-20).
The mol ratio of the boronate s-triazine of class graphene-like silica and 2,4,6- tri- is 1：(10-15).
The preparing raw material also includes the additive of 0.1-5 parts by weight；The additive includes aluminium hydroxide, hydroxide
Magnesium, calcium aluminate, triphenyl phosphate, tricresyl phosphate, phosphoric acid bisphenol-A-bis- diphenyl esters and phosphoric acid resorcinol-bis- diphenyl esters,
APP, polyphosphoric acid melamine, polyphosphoric acid piperazine, orthophosphoric acid piperazine, melamine pyrophosphate, piperazine pyrophosphate, poly- phosphorus
One or more in sour melamine, orthophosphoric acid melamine, calcium phosphate and magnesium phosphate.
Another aspect of the invention provides the method for preparing a kind of flame-retardant thermoplastic elastomer composition,
(1) by described raw material, after mixing by weight, through double-screw extruding pelletizing；
(2) product that step (1) obtains is placed in 60-80 DEG C of hot air type hopper and dries 2-4 hours；
(3) by step (2) obtained by product, in 170 DEG C of -220 DEG C of vacuum injections into mould, and under vacuum,
Kept for temperature 0.5-20 hours, then cooled and solidified, obtain flame-retardant thermoplastic elastomer.
Sulfonated SEBS：
Term " sulfonated SEBS " used herein refers to, to SEBS progress sulfonation processing, make it possess certain sulfonation
Degree, such as the concentrated sulfuric acid, oleum or acetyl sulfonate can be used as sulfonated reagent, it is preferable that sulfonated SEBS can use
It is prepared by following methods：
(1) under conditions of ice bath, 100ml 1 is added into three-necked bottle, 2- dichloroethanes (DEC), is then added
0.1mol acetic anhydride, is at the uniform velocity stirred, and when its equalized temperature is to less than 5 DEG C, is added dropwise to the 0.11mol concentrated sulfuric acid, reaction
Ice bath is withdrawn after 30min, 10min is quickly stirred at room temperature, that is, obtains fresh acetyl sulfonate.
(2) 5g SEBS are added in the three-necked flask equipped with 160mL DCE, nitrogen charging, 45 DEG C of water-baths, electric stirring, returned
Stream, then adding 20mL hexamethylene makes it fully dissolve, until solution is transparent, then adds freshly prepared acetyl sulfonate
5-30mL carries out sulfonating reaction as sulfonating agent, and 50mL isopropanol stopped reactions are added after reacting 5h.
(3) 40 DEG C of mix products are evaporated under reduced pressure out mixed solvent, obtain viscous solid product, are precipitated using aqueous phase transfer method
After pour out, subsequent 90 DEG C are boiled a few hours, until a small amount of solvent evaporates into the greatest extent, cooling, washing and are filtered, until during filtrate is
Property, filter residue is fully dried at 40 DEG C, obtained in a vacuum.
In above-mentioned preparation method, by controlling the dosage of acetyl sulfonate, the sulfonation of sulfonated SEBS can be effectively controlled
Degree, such as dosage is 10mL and 23mL, the ion exchange capacity of sulfonated SEBS reclaimed materials is respectively 0.4 and 1.5.
In one embodiment, the ion exchange capacity of the sulfonated SEBS is 0.4-1.5；Preferably, the sulfonation
SEBS ion exchange capacity is 0.8-1.4；It is highly preferred that the ion exchange capacity of the sulfonated SEBS is 1.0-1.3；It is optimal
Selection of land, the ion exchange capacity of the sulfonated SEBS is 1.2.
Term " ion exchange capacity " in the application refers in 1 gram of sulfonated SEBS, mM number of sulfonic acid group.
MAH-g-PP：
Term " MAH-g-PP " refers to maleic anhydride (MAH) graft modification polypropylene (PP) in this specification, is used as this hair
The MAH-g-PP of bright raw material is not particularly limited, and can be commercially available acquisition, can also pass through solwution method, supercritical CO2Solwution method,
The method synthesis well-known to those skilled in the art such as fusion method, radiation method and solid phase method obtains.Wherein, solwution method progress PP connects
During branch MAH, the graft reaction time is grown, and grafting efficiency is low, it is necessary to consume a large amount of poisonous, flammable solvents, production cost is high, to human body
Injury is big, pollutes environment, takes up an area big, it is difficult to realize continuous operation.It is therefore preferable that using fusion method.
For example, MAH-g-PP is prepared with fusion method：Styrene and initiator cumyl peroxide are mixed, it is molten
Solution, it is made into the styrene solution of initiator.By polypropylene and maleic anhydride mixing resulting mixture, by polypropylene and maleic anhydride
Mixture input double screw extruder, after its melting after, by the styrene solution of initiator double screw extruder different spiral shells
The continuous metering input of cylinder section, carries out melting graft reaction, obtains MAH-g-PP.
In the MAH-g-PP, MAH grafting rates are 1.5%-4.5%；Preferably, MAH grafting rate is 2.3%-
4.0%, it is further preferred that MAH grafting rate is 3.5%.
MAH grafting rates are tested using acid-base titration in embodiment and comparative example in the present invention.
The main process of acid-base titration：Weigh 0.5g polypropylene grafted maleic anhydrides to be dissolved in the hot dimethylbenzene of 50mL, treat
The NaOH- ethanol solutions that 10mL 0.1mol/L are added in backward system are completely dissolved, flows back 10 minutes, makes in maleic anhydride
Anhydride group fully reacts with alkali, after add micro deionized water (50 μ l) or pyridine/DMF while hot into system, promote acid
Acid anhydride is hydrolyzed into carboxylic acid.3 drop phenolphthalein indicators are added simultaneously, afterwards with hydrochloric acid/isopropanol titration to terminal.If HCl/ aqueous isopropanols
Concentration is C (mol/L), titrates M (g) sample, consumes volume V1 (mL) solution, and blank titration consumption V2 (mL), grafting rate G are pressed
Formula calculates：
G=C (V2-V1) × 98/ (2 × M × 1000) × 100%
98 be MAH molecular weight in formula.
Heretofore described MAH-g-PP can also be commercially available.
White oil：
White oil is the cycloalkane and alkane mixture of the mixture, predominantly saturation of refining liquid hydrocarbon obtained by oil,
Crude oil through normal pressure and vacuum fractionation, solvent extraction and dewaxing, hydrofinishing and obtain.White oil improves two-phase mainly as lubricant
Compatibility.
White oil is not particularly limited the application, commercially available acquisition.Preferably, the white of standard Q/MSH32-2009 is met
Oil.
Class graphene-like silica：
In the present invention, the term " class graphene-like silica " is the titanium dioxide with similar graphene platelet shape
Silicon.
As a kind of embodiment, heretofore described class graphene-like silica can be prepared into by following methods
Arrive：Appropriate graphene oxide is dissolved in DMF, adds appropriate 3- (isobutene acyl-oxygen) propyl group front three
TMOS monomer, then lead to nitrogen, add initiator under agitation；At 65 DEG C after water-bath 36h, centrifugation, dry, product is put
10h is heat-treated at 700 DEG C, obtains class graphene-like silica.
In the present invention, the graphene oxide is product of the powdered graphite after chemical oxidation and stripping, graphene oxide
Be single atomic layer, some tens of pm can be expanded on lateral dimension at any time, therefore, the general chemistry of its construct trans and
The typical size of material science.Graphene oxide can be considered a kind of flexible material of non-traditional kenel, have polymer, colloid,
Film, and the characteristic of amphiphatic molecule.After oxidation processes, graphite oxide still keeps the layer structure of graphite, but each
Many epoxide functional groups are introduced on the graphene monolithic of layer.Graphene oxide is typically aoxidized by graphite and obtained through strong acid.Mainly
There are three kinds of methods for preparing graphite oxide：Brodie methods, Staudenmaier methods and Hummers methods.The wherein system of Hummers methods
The ageing of standby process preferably and in preparation process also compares safety relatively, is one kind the most frequently used at present.It uses dense sulphur
Potassium permanganate in acid has derivative carboxylic acid group and in the plane at edge with after the oxidized reaction of powdered graphite, obtain brown
The predominantly graphite flake of phenolic hydroxyl group and epoxide group, this graphene layers can be stirred vigorously stripping through ultrasound or high shear and be
Graphene oxide, and stable, the single-layer graphene oxide suspension of sundown is formed in water.Because conjugate network is by tight
The functionalization of weight, graphene oxide thin slice have the speciality of insulation.Partial reduction can be carried out through reduction treatment, obtains chemical modification
Graphene platelet.At present, graphene oxide new method is prepared to have emerged in an endless stream, be generally divided into top-down approach and
The major class of Bottom-up approach two.The former thinking is to split crystalline flake graphite etc. to prepare graphene oxide, with changing for traditional three methods
It is representative to enter method, in addition to method for splitting (breaking) CNT etc..The latter is the method synthesized with various carbon sources, is had
Body method is multifarious, and species is various.
In the present invention, the thickness of the class graphene-like silica is 1-5nm.
In the present invention, the class graphene-like silica is similar graphene oxide flake structure.
Hyperbranched poly triazine radical phenyl ring：
Heretofore described hyperbranched poly triazine radical phenyl ring, it is by the bromo- 1H- benzimidizole derivatives of 4,7- bis- and 2,4,6-
Three boronate s-triazine obtain by Suzuki coupling reactions, as follows shown in course of reaction：
The symbolFor the repeat unit with hyperbranched poly triazine radical phenyl ring.
In Suzuki reactions, by lot of experiment validation, using palladium complex as catalyst, the palladium complex can be with
It is zeroth order palladium complex, for example, tetrakis triphenylphosphine palladium.Can also be non-zero valence palladium complex, for example, palladium, dichloride
Palladium, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride.
The organic solvent can be one kind in ethanol, 1,4- dioxane, DMF, toluene, tetrahydrofuran.
The alkali can be one kind in barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, cesium fluoride, potassium phosphate.
KOAc is most suitable weak base catalyst, and stronger base catalyst can make starting aryl halogen that self-coupling reaction occur；
In Suzuki reactions, preferable solvent is DMSO and DMF, it is also an option that dioxane and tuluene；As whole reaction
Catalyst, Pd (dppf) Cl2Typically can preferable result.
In Suzuki reactions, the addition of described 2,4,6- tri- boronate triazines is excessive relative to halogenated aryl hydrocarbon
10%, because deboration can cause the loss of aryl boric acid；But if 2,4,6- tri- boronate triazines are first converted into
Ester, coupling reaction is used further to, the loss of reaction mesoboric acid can be reduced.
In the present invention, the bromo- 1H- benzimidizole derivatives of 4, the 7- bis- and 2, the mol ratio of 4,6- tri- boronate s-triazine
For 1：(1.1-2.2), preferably 1：1.8.
The preparation of the boronate triazines of 2,4,6- tri- can be prepared into by any method well known by persons skilled in the art
Arrive.
Such as：
Wherein, R is one kind in methyl, ethyl, propyl group, butyl；X is Cl or Br, preferably Br.
The boronate s-triazine of 2,4,6- tri- can also be commercially available.
The preparation of the bromo- 1H- benzimidizole derivatives of 4,7- bis- can be prepared using following methods：
(1) diazosulfides of 5g 2,1,3- are heated to reflux in 15ml HBr solution, be added dropwise simultaneously in stirring
5.7ml Br230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, will be more with the saturated solution of sodium hydrogensulfite
Remaining Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
In the present invention, the bromo- 1H- benzimidazoles of 4,7- bis- can also be commercially available.
In the present invention, both with imidazole group ionomer can occur for the sulfonic acid group in sulfonated SEBS, again can be with group
Fu Ke-acylation reaction occurs for the phenyl ring of the electron rich in compound, improves crosslink density, thus provides the beneficial skill of the present invention
Art effect.
Class graphene-like silica and hyperbranched poly triazine radical benzimidazole it is compound：
In the present invention, class graphene-like silica and hyperbranched poly the triazine radical phenyl ring it is compound, be class stone first
The black boronate s-triazine of alkene shape silica and monomer 2,4,6- tri- is reacted, i.e. the surface in class graphene-like silica
The upper boronate s-triazine of grafted monomers 2,4,6- tri-, the class stone that then will be grafted again with the boronate s-triazine of monomer 2,4,6- tri-
Black alkene shape silicon dioxide is added in the Suzuki coupling reactions of 2,4,6- tri- boronate s-triazine and Isosorbide-5-Nitrae-phenyl-dihalide derivative,
Further recombination reaction is carried out, as a result can obtain the surface grafting dissaving structure in class graphene-like silica
Poly- triazine radical phenyl ring.
In the present invention, the reaction of the boronate s-triazine of class graphene-like silica and monomer 2,4,6- tri- can be with
Reacted using the hydroxyl on the hydroxyl and the boronate s-triazine of monomer 2,4,6- tri- of class graphene-like silica surface.Institute
Stating reaction can be prepared using any method well known by persons skilled in the art.For example, the boric acid of monomer 2,4,6- tri-
Base s-triazine is slightly excessive, adds appropriate class graphene-like silica and the concentrated sulfuric acid, heating response, obtains class graphene-like dioxy
Many boronate s-triazine of monomer 2,4,6- tri- are grafted on the surface of SiClx.
In the present invention, the reaction of the boronate s-triazine of class graphene-like silica and monomer 2,4,6- tri-, also may be used
First to handle class graphene-like silica surface, make its surface with the group that can be reacted with boronate, such as
Hydroxyl, aldehyde radical etc., are then further reacted again.
Polymeric material is the macromolecular organic compound containing many carbon, protium, in certain temperature and oxygen
Under effect, violent ignition can be caused.The combustion process is, after polymeric material is heated, heat conduction enters material
Inside, material absorb heat melting first；Temperature continues to raise, and the key of some heat endurances difference starts to be broken, the thermal decomposition of polymer
Start and discharge fuel gas, when fuel gas reaches finite concentration with temperature, can be reacted with oxygen, ignition occurs；
Heat caused by burning can be fed back to undecomposed solid combustible by gas-phase combustion again, be further exacerbated by the melting of polymer with
Decompose, produce more imflammable gas, aggravate burning.
After the fire retardant is added among TPE systems, when system is in heated combustion, the fire retardant can form one
Layer froth bed, the froth bed can play a part of heat-insulated, oxygen barrier, suppression cigarette, and prevent molten drop from producing.
Meanwhile by substantial amounts of experiment, the present inventor is found surprisingly that, because fire retardant has hyperbranched knot
When structure make it that the addition of the fire retardant is seldom, it is possible to good flame retardant effect is played, simultaneously because silica is in itself
Excellent characteristic, outside plus the form of its class graphene-like, not only can it is bigger, more effectively play flame retardant effect, improve heat
Stability, while the mechanical property of system can be improved again；Outside plus substantial amounts of carboxyl is contained on the dissaving structure, in height
Under conditions of temperature and vacuum dehydration, friedel-crafts acylation can occur with the phenyl ring in sulfonated SEBS on styrene units, from
And further crosslinking occurs, improve the tensile strength of whole composite.
Other：
In a kind of flame-retardant thermoplastic elastomer composition of the present invention, it can suitably coordinate filler as needed to make
With.As packing material, be not particularly limited, can be inorganic filler (for example, talcum, calcium carbonate and calcined kaolin),
Organic filler (for example, fiber, wood powder and cellulose powder), antioxidant (for example, phenol system, sulphur system, phosphorus system, lactone system and
The antioxidant of vitamin system), weathering stabilizers, UV absorbents (for example, enumerate BTA system, three diamines (tridiamine) system,
N- anilides system and benzophenone series UV absorbents), heat stabilizer, light stabilizer (such as, hindered amine as light stabilizer and benzoic acid
Ester type light stabilizer), antistatic additive, nucleator, pigment, adsorbent (for example, metal oxide), metal chloride (such as, chlorine
Change iron and calcium chloride), hydrotalcite, aluminate, lubricant (for example, aliphatic acid, higher alcohol, aliphatic amides and aliphatic (acid) ester) and silicon
Siloxane compound.
Another aspect provides the method for preparing a kind of flame-retardant thermoplastic elastomer composition, its feature
It is,
(1) by described raw material, after mixing by weight, through double-screw extruding pelletizing；
(2) product that step (1) obtains is placed in 60-80 DEG C of hot air type hopper and dries 2-4 hours；
(3) by step (2) obtained by product, in 170 DEG C of -220 DEG C of vacuum injections into mould, and under vacuum,
Kept for temperature 0.5-20 hours, then cooled and solidified, obtain flame-retardant thermoplastic elastomer.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used be all it is commercially available, purchase the limited public affairs of Chinese medicines group chemical reagent
Department, and number used in following material is parts by weight.
Raw material：
A1：Sulfonated SEBS (ion exchange capacity 0.4)
A2：Sulfonated SEBS (ion exchange capacity 1.2)
A3：Sulfonated SEBS (ion exchange capacity 1.5)
A4：SEBS (non-sulfonated)
B1：MAH-g-PP (MAH grafting rates 1.5%)
B2：MAH-g-PP (MAH grafting rates 3.5%)
B3：MAH-g-PP (MAH grafting rates 4.5%)
C：Fire retardant
Wherein, class graphene-like silica and 2, the mol ratio of 4, the 6- tri- positive triazines of boronate are designated as X
Table 1
| R1 | X | |
| C1 | Carboxyl | 1：13 |
| C2 | Carboxyl | 1：17 |
| C3 | Hydroxyl | 1：9 |
| C4 | Hydroxyl | 1：10 |
| C5 | Amino | 1：5 |
| C6 | Amino | 1：15 |
| C7 | Sulfonic group | 1：20 |
| C8 | Sulfonic group | 1：13 |
C1 preparation method：
[1] synthetic route of the bromo- 5- carboxyls -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- carboxyls -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, in stirring simultaneously
5.7ml Br is added dropwise230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, with the saturated solution of sodium hydrogensulfite
By unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 13 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C2 preparation method：
[1] synthetic route of the bromo- 5- carboxyls -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- carboxyls -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, in stirring simultaneously
5.7ml Br is added dropwise230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, with the saturated solution of sodium hydrogensulfite
By unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 17 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C3 preparation method：
[1] synthetic route of the bromo- 5- hydroxyls -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- hydroxyls -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, in stirring simultaneously
5.7ml Br is added dropwise230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, with the saturated solution of sodium hydrogensulfite
By unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 9 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C4 preparation method：
[1] synthetic route of the bromo- 5- hydroxyls -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- hydroxyls -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, in stirring simultaneously
5.7ml Br is added dropwise230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, with the saturated solution of sodium hydrogensulfite
By unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 10 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C5 preparation method：
[1] synthetic route of the bromo- 5- amino -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- amino -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, in stirring simultaneously
5.7ml Br is added dropwise230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, with the saturated solution of sodium hydrogensulfite
By unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 5 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C6 preparation method：
[1] synthetic route of the bromo- 5- amino -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- amino -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, in stirring simultaneously
5.7ml Br is added dropwise230min；Mixture is flowed back 3 hours, room temperature is subsequently cooled to, with the saturated solution of sodium hydrogensulfite
By unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 15 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C7 preparation method：
[1] synthetic route of the bromo- 5- sulfonic groups -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- sulfonic groups -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, it is same in stirring
When be added dropwise 5.7ml Br230min；Mixture is flowed back 3 hours, is subsequently cooled to room temperature, it is molten with the saturation of sodium hydrogensulfite
Liquid is by unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 20 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
C8 preparation method：
[1] synthetic route of the bromo- 5- sulfonic groups -1H- benzimidazoles of 4,7- bis-：
(1) 5g 5- sulfonic groups -2,1,3- diazosulfides are heated to reflux in 15ml HBr solution, it is same in stirring
When be added dropwise 5.7ml Br230min；Mixture is flowed back 3 hours, is subsequently cooled to room temperature, it is molten with the saturation of sodium hydrogensulfite
Liquid is by unnecessary Br2Wash away, be filtrated to get solid (1)；
(2) product in 3.5g solids (1) is taken to be dissolved in 400ml EtOH and 40ml THF, under conditions of nitrogen,
8.11g sodium borohydride is added portionwise, is stirred 10 minutes at 0 DEG C, 3 hours is then stirred at room temperature again；It is removed under reduced pressure
After solvent, by residue 150ml Et2O dilutes, and is dried with salt water washing, magnesium sulfate, obtains solid (2)；
(3) 2.11g solids (2) are dissolved in 70ml dichloromethane, then add 1.06ml HC in the solution
(OEt)3, stir 10 minutes, then add 20mg camphorsulfonic acid as catalyst, after reacting 1 hour, filtering, wash, be dry
It is dry, produce product.
Specific course of reaction is as shown below：
[2] reaction of class graphene-like silica and the boronate s-triazine of monomer 2,4,6- tri-
By the class graphene-like silica of 1 parts by weight and the boronate s-triazine of the monomer 2,4,6- of 13 parts by weight tri- dense
Under conditions of sulfuric acid is as catalyst, heating response, product (2) is obtained；
[3] class graphene-like silica and hyperbranched poly triazine radical benzimidazole are carried out compound
Into 50 milliliters of three neck round bottom, by product (2), monomer 2,4, the boronate s-triazine of 6- tri- and 4,7- bis-
Bromo- 5- carboxyls -1H- benzimidazoles are in KOAc as weak base catalyst, and DMSO is solvent, Pd (dppf) Cl2For the bar of catalyst
Under part, nitrogen is passed through 30 minutes, then oil bath heating 5 hours at 85 DEG C, reactant mixture is then cooled to room temperature, and with
Water dilutes, and generation precipitation, is then diluted with water and dries, produce.
D：White oil
E：Other
The specific embodiment of table 2
Method of testing
Above-described embodiment 1-15 is prepared into strips, and tested, method of testing is as follows：
Tensile property：Tensile strength and elongation at break are measured according to JIS K6251.
Anti-flammability：It is measured according to UL94 standards.
Test result is shown in Table 3.
Table 3
Data above can be seen that with without using sulfonated SEBS, fire retardant product compared with, the material for preparing of the present invention exists
While possessing high intensity, also with good anti-flammability, advantageous effects of the invention are thus provided.Foregoing example
It is merely illustrative, some features of the feature for explaining the disclosure.Appended claim is intended to require what is be contemplated that
Scope as wide as possible, and embodiments as presented herein is only the implementation according to the selection of the combination of all possible embodiment
The explanation of mode.Therefore, the purpose of applicant is appended claim not by the selection of the example of the feature of the explanation present invention
Limitation.And the progress in science and technology will be formed and is not presently considered possible due to the inaccuracy of language performance
Equivalent or son are replaced, and these changes should also be interpreted by appended claim covering in the conceived case.
Claims (10)
- A kind of 1. flame-retardant thermoplastic elastomer composition, it is characterised in that by weight, comprising：The sulfonated SEBS of 100 parts by weight；The MAH-g-PP of 50-60 parts by weight；The white oil of 10-30 parts by weight；WithThe fire retardant of 5-15 parts by weight；Wherein, the fire retardant is that class graphene-like silica and hyperbranched poly triazine radical benzimidazole carry out compound be prepared into Arrive；The structure such as formula [1] of the hyperbranched poly triazine radical benzimidazole, formula [1] structure are：Wherein, R1For one kind in carboxyl, hydroxyl, amino, sulfonic group；The symbolFor the repeat unit with formula [1] representation.
- 2. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, it is characterised in that the sulfonated SEBS Ion exchange capacity is 0.4-1.5.
- 3. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, it is characterised in that the MAH-g-PP's Grafting rate is 1.5%-4.5%.
- A kind of 4. flame-retardant thermoplastic elastomer composition according to claim 1, it is characterised in that the poly- triazine radical benzene And imidazoles, by the bromo- 1H- benzimidizole derivatives of 4,7- bis- and 2, the reaction of 4,6- tri- boronate s-triazine obtains, and 4, the 7- bis- The mol ratio of the bromo- boronate s-triazine of 1H- benzimidizole derivatives and 2,4,6- tri- is 1：(1.1-2.2).
- A kind of 5. flame-retardant thermoplastic elastomer composition according to claim 1, it is characterised in that the class graphene-like Silica and the compound of hyperbranched poly triazine radical benzimidazole are by class graphene-like silica and the boric acid of 2,4,6- tri- Base s-triazine reacts, then is obtained with the hyperbranched reaction of the bromo- 1H- benzimidizole derivatives of 4,7- bis-.
- A kind of 6. flame-retardant thermoplastic elastomer composition according to claim 5, it is characterised in that the class graphene-like Silica is by including graphene oxide, N,N-dimethylformamide, 3- (isobutene acyl-oxygen) propyl trimethoxy silicanes and idol The raw material of nitrogen bis-isobutyronitrile is prepared.
- A kind of 7. flame-retardant thermoplastic elastomer composition according to claim 5, it is characterised in that the class graphene-like The mol ratio of silica and the boronate s-triazine of 2,4,6- tri- is 1：(5-20).
- A kind of 8. flame-retardant thermoplastic elastomer composition according to claim 5, it is characterised in that the class graphene-like The mol ratio of silica and the boronate s-triazine of 2,4,6- tri- is 1：(10-15).
- 9. a kind of flame-retardant thermoplastic elastomer composition according to claim 1, it is characterised in that the composition also wraps Include the additive of 0.1-5 parts by weight：Talcum, calcium carbonate, wood powder, cellulose powder, weathering stabilizers, enumerate BTA system UV absorb Agent, heat stabilizer, aminobenzoate type light stabilizer, antistatic additive, aluminate, lubricant, one kind in silicone compounds or It is a variety of.
- 10. a kind of method for preparing a kind of flame-retardant thermoplastic elastomer composition as described in claim any one of 1-9, it is special Sign is,(1) by the raw material of any one of claim 1-9 claim, after mixing by weight, through double-screw extruding pelletizing；(2) product that step (1) obtains is placed in 60-80 DEG C of hot air type hopper and dries 2-4 hours；(3) by step (2) obtained by product, in 170 DEG C of -220 DEG C of vacuum injections into mould, and under vacuum, keep Temperature 0.5-20 hours, then cool and solidify, obtain flame-retardant thermoplastic elastomer.
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| CN101629007A (en) * | 2009-08-27 | 2010-01-20 | 华南理工大学 | Low smoke non-halogen flame retardant thermoplastic elastomer composite material and preparation method thereof |
| CN101747579A (en) * | 2008-12-22 | 2010-06-23 | 上海日之升新技术发展有限公司 | Low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method thereof |
| CN103540075A (en) * | 2012-07-18 | 2014-01-29 | 苏州朗创化工有限公司 | Highly flame-retardant TPE (Thermoplastic Polyurethane Elastomer) material |
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| CN101469100A (en) * | 2008-06-19 | 2009-07-01 | 上海化工研究院 | Halogen-free expansion type flame-retarding composition based on thermoplastic elastomer SEBS and process for the preparation thereof |
| CN101747579A (en) * | 2008-12-22 | 2010-06-23 | 上海日之升新技术发展有限公司 | Low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method thereof |
| CN101629007A (en) * | 2009-08-27 | 2010-01-20 | 华南理工大学 | Low smoke non-halogen flame retardant thermoplastic elastomer composite material and preparation method thereof |
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