CN110343205A - Side group functionalized polyisobutylene base thermoplastic elastomer and preparation method thereof - Google Patents
Side group functionalized polyisobutylene base thermoplastic elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN110343205A CN110343205A CN201810298752.9A CN201810298752A CN110343205A CN 110343205 A CN110343205 A CN 110343205A CN 201810298752 A CN201810298752 A CN 201810298752A CN 110343205 A CN110343205 A CN 110343205A
- Authority
- CN
- China
- Prior art keywords
- imidazoles
- group
- methylimidazole
- thermoplastic elastomer
- imidazole
- 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.)
- Pending
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 49
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000026030 halogenation Effects 0.000 claims abstract description 12
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 12
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 30
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 19
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 229940035893 uracil Drugs 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002460 imidazoles Chemical class 0.000 claims description 12
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- UHDGCWIWMRVCDJ-UHFFFAOYSA-N 1-beta-D-Xylofuranosyl-NH-Cytosine Natural products O=C1N=C(N)C=CN1C1C(O)C(O)C(CO)O1 UHDGCWIWMRVCDJ-UHFFFAOYSA-N 0.000 claims description 8
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 claims description 8
- UHDGCWIWMRVCDJ-PSQAKQOGSA-N Cytidine Natural products O=C1N=C(N)C=CN1[C@@H]1[C@@H](O)[C@@H](O)[C@H](CO)O1 UHDGCWIWMRVCDJ-PSQAKQOGSA-N 0.000 claims description 8
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 claims description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 8
- UHDGCWIWMRVCDJ-ZAKLUEHWSA-N cytidine Chemical compound O=C1N=C(N)C=CN1[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O1 UHDGCWIWMRVCDJ-ZAKLUEHWSA-N 0.000 claims description 8
- 229960002949 fluorouracil Drugs 0.000 claims description 8
- 150000003918 triazines Chemical class 0.000 claims description 8
- SPGPGBWICPNRSN-UHFFFAOYSA-N 1-iodoimidazole Chemical class IN1C=CN=C1 SPGPGBWICPNRSN-UHFFFAOYSA-N 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- FDGQSTZJBFJUBT-UHFFFAOYSA-N hypoxanthine Chemical group O=C1NC=NC2=C1NC=N2 FDGQSTZJBFJUBT-UHFFFAOYSA-N 0.000 claims description 6
- 239000002777 nucleoside Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- VYDWQPKRHOGLPA-UHFFFAOYSA-N 5-nitroimidazole Chemical compound [O-][N+](=O)C1=CN=CN1 VYDWQPKRHOGLPA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003835 nucleoside group Chemical group 0.000 claims description 5
- 238000007500 overflow downdraw method Methods 0.000 claims description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 4
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 claims description 4
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 4
- HIDCNJIBRZBEPN-UHFFFAOYSA-N 2,4,5-triiodo-1h-imidazole Chemical class IC1=NC(I)=C(I)N1 HIDCNJIBRZBEPN-UHFFFAOYSA-N 0.000 claims description 4
- MXFMPTXDHSDMTI-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-benzimidazole Chemical compound C1=CC=C2NC(C(F)(F)F)=NC2=C1 MXFMPTXDHSDMTI-UHFFFAOYSA-N 0.000 claims description 4
- BOJZBRDIZUHTCE-UHFFFAOYSA-N 2-chloro-5-nitro-1h-imidazole Chemical compound [O-][N+](=O)C1=CN=C(Cl)N1 BOJZBRDIZUHTCE-UHFFFAOYSA-N 0.000 claims description 4
- AGUNPFIFLDXKPR-UHFFFAOYSA-N 2-trityl-1h-imidazole Chemical compound C1=CNC(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=N1 AGUNPFIFLDXKPR-UHFFFAOYSA-N 0.000 claims description 4
- MCMFEZDRQOJKMN-UHFFFAOYSA-O 3-butyl-1h-imidazol-3-ium Chemical compound CCCCN1C=C[NH+]=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-O 0.000 claims description 4
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 claims description 4
- DGHAOTHIDTUSJY-UHFFFAOYSA-N 4-(imidazol-1-ylmethyl)aniline Chemical class C1=CC(N)=CC=C1CN1C=NC=C1 DGHAOTHIDTUSJY-UHFFFAOYSA-N 0.000 claims description 4
- LVOASPZGXNAHJI-UHFFFAOYSA-N 4-imidazol-1-ylaniline Chemical class C1=CC(N)=CC=C1N1C=NC=C1 LVOASPZGXNAHJI-UHFFFAOYSA-N 0.000 claims description 4
- LMNPKIOZMGYQIU-UHFFFAOYSA-N 5-(trifluoromethyl)-1h-pyrimidine-2,4-dione Chemical compound FC(F)(F)C1=CNC(=O)NC1=O LMNPKIOZMGYQIU-UHFFFAOYSA-N 0.000 claims description 4
- XEKNACRTWJHOCE-UHFFFAOYSA-N 6-Phenyl-2-thiouracil Chemical compound O=C1NC(S)=NC(C=2C=CC=CC=2)=C1 XEKNACRTWJHOCE-UHFFFAOYSA-N 0.000 claims description 4
- PKUFNWPSFCOSLU-UHFFFAOYSA-N 6-chloro-1h-pyrimidine-2,4-dione Chemical compound ClC1=CC(=O)NC(=O)N1 PKUFNWPSFCOSLU-UHFFFAOYSA-N 0.000 claims description 4
- IYCFUBICJBYSCE-UHFFFAOYSA-N I(=O)(=O)O.C(C)N1CN(C=C1)C Chemical compound I(=O)(=O)O.C(C)N1CN(C=C1)C IYCFUBICJBYSCE-UHFFFAOYSA-N 0.000 claims description 4
- VIHYIVKEECZGOU-UHFFFAOYSA-N N-acetylimidazole Chemical compound CC(=O)N1C=CN=C1 VIHYIVKEECZGOU-UHFFFAOYSA-N 0.000 claims description 4
- GELQGNSEMRPIQJ-UHFFFAOYSA-N [[4,6-bis(dimethylamino)-1,3,5-triazin-2-yl]-methylamino]methanol Chemical compound CN(C)C1=NC(N(C)C)=NC(N(C)CO)=N1 GELQGNSEMRPIQJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 4
- UUVWYPNAQBNQJQ-UHFFFAOYSA-N hexamethylmelamine Chemical compound CN(C)C1=NC(N(C)C)=NC(N(C)C)=N1 UUVWYPNAQBNQJQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 4
- VKDVOWJBMGDDQM-UHFFFAOYSA-N quinolin-4-amine 1,3,5-triazine Chemical compound C1=NC=NC=N1.C1=CC=C2C(N)=CC=NC2=C1 VKDVOWJBMGDDQM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 229940048102 triphosphoric acid Drugs 0.000 claims description 4
- 229940075420 xanthine Drugs 0.000 claims description 4
- FLYGQJXMRPZYHQ-UHFFFAOYSA-N 1-[(4-nitrophenyl)methyl]imidazole Chemical class C1=CC([N+](=O)[O-])=CC=C1CN1C=NC=C1 FLYGQJXMRPZYHQ-UHFFFAOYSA-N 0.000 claims description 3
- AFNRMRFWCAJQGP-UHFFFAOYSA-N 2,5,6-trimethyl-1h-benzimidazole Chemical compound CC1=C(C)C=C2NC(C)=NC2=C1 AFNRMRFWCAJQGP-UHFFFAOYSA-N 0.000 claims description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 3
- HXBGOHZLZCFWLH-OERIEOFYSA-N 4-amino-1-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]pyrimidin-2-one;hydrate Chemical compound O.O=C1N=C(N)C=CN1[C@@H]1O[C@H](CO)[C@@H](O)C1 HXBGOHZLZCFWLH-OERIEOFYSA-N 0.000 claims description 3
- OVONXEQGWXGFJD-UHFFFAOYSA-N 4-sulfanylidene-1h-pyrimidin-2-one Chemical compound SC=1C=CNC(=O)N=1 OVONXEQGWXGFJD-UHFFFAOYSA-N 0.000 claims description 3
- KSNXJLQDQOIRIP-UHFFFAOYSA-N 5-iodouracil Chemical compound IC1=CNC(=O)NC1=O KSNXJLQDQOIRIP-UHFFFAOYSA-N 0.000 claims description 3
- VNTFEWXYAOATFA-UHFFFAOYSA-N 6-bromo-2h-1,2,4-triazine-3,5-dione Chemical compound BrC1=NNC(=O)NC1=O VNTFEWXYAOATFA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000003230 pyrimidines Chemical class 0.000 claims description 3
- 210000002700 urine Anatomy 0.000 claims description 3
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 claims description 2
- AGGRGODMKWLSDE-UHFFFAOYSA-N 1-[2,4,6-tri(propan-2-yl)phenyl]sulfonylimidazole Chemical class CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1S(=O)(=O)N1C=NC=C1 AGGRGODMKWLSDE-UHFFFAOYSA-N 0.000 claims description 2
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 2
- UWRJWMLKEHRGOH-UHFFFAOYSA-N 2-bromo-5-nitro-1h-imidazole Chemical compound [O-][N+](=O)C1=CN=C(Br)N1 UWRJWMLKEHRGOH-UHFFFAOYSA-N 0.000 claims description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical class C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 claims description 2
- IROWWTVZNHKLLE-UHFFFAOYSA-N 6-(trifluoromethyl)-1h-pyrimidine-2,4-dione Chemical compound FC(F)(F)C1=CC(=O)NC(=O)N1 IROWWTVZNHKLLE-UHFFFAOYSA-N 0.000 claims description 2
- UGQMRVRMYYASKQ-UHFFFAOYSA-N Hypoxanthine nucleoside Natural products OC1C(O)C(CO)OC1N1C(NC=NC2=O)=C2N=C1 UGQMRVRMYYASKQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- XBCXJKGHPABGSD-UHFFFAOYSA-N 1-methyluracil Chemical compound CN1C=CC(=O)NC1=O XBCXJKGHPABGSD-UHFFFAOYSA-N 0.000 claims 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims 1
- XMWPTVMTXKJONE-UHFFFAOYSA-N 4,5-diiodo-1h-imidazole Chemical class IC=1N=CNC=1I XMWPTVMTXKJONE-UHFFFAOYSA-N 0.000 claims 1
- YPHHKFWHAPFOFK-UHFFFAOYSA-N 6,6-dimethylhepta-1,3-diene Chemical compound CC(C)(C)CC=CC=C YPHHKFWHAPFOFK-UHFFFAOYSA-N 0.000 claims 1
- VNQDUDYVRUASAA-UHFFFAOYSA-N CC=1C(NC(NC1)=O)=O.NC=1C=CC=C(C1N)C=CC1=CC=CC=C1 Chemical compound CC=1C(NC(NC1)=O)=O.NC=1C=CC=C(C1N)C=CC1=CC=CC=C1 VNQDUDYVRUASAA-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims 1
- 229950000329 thiouracil Drugs 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 238000013016 damping Methods 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 229920005549 butyl rubber Polymers 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 39
- 230000005540 biological transmission Effects 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- IQFYYKKMVGJFEH-XLPZGREQSA-N Thymidine Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@H](CO)[C@@H](O)C1 IQFYYKKMVGJFEH-XLPZGREQSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 2
- DWRXFEITVBNRMK-UHFFFAOYSA-N Beta-D-1-Arabinofuranosylthymine Natural products O=C1NC(=O)C(C)=CN1C1C(O)C(O)C(CO)O1 DWRXFEITVBNRMK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IQFYYKKMVGJFEH-UHFFFAOYSA-N beta-L-thymidine Natural products O=C1NC(=O)C(C)=CN1C1OC(CO)C(O)C1 IQFYYKKMVGJFEH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920005555 halobutyl Polymers 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000306 recurrent effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940104230 thymidine Drugs 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- GEWRKGDRYZIFNP-UHFFFAOYSA-N 1h-1,3,5-triazine-2,4-dione Chemical compound OC1=NC=NC(O)=N1 GEWRKGDRYZIFNP-UHFFFAOYSA-N 0.000 description 1
- IEJPPSMHUUQABK-UHFFFAOYSA-N 2,4-diphenyl-4h-1,3-oxazol-5-one Chemical compound O=C1OC(C=2C=CC=CC=2)=NC1C1=CC=CC=C1 IEJPPSMHUUQABK-UHFFFAOYSA-N 0.000 description 1
- AQYKIROTAGYYQK-UHFFFAOYSA-N 5,5-dimethyl-3-methylidenehex-1-ene Chemical compound CC(C)(C)CC(=C)C=C AQYKIROTAGYYQK-UHFFFAOYSA-N 0.000 description 1
- KKKKQVZKEFWOFS-UHFFFAOYSA-N 5-amino-1-methylpyrimidine-2,4-dione Chemical compound CN1C=C(N)C(=O)NC1=O KKKKQVZKEFWOFS-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- WREGKURFCTUGRC-POYBYMJQSA-N Zalcitabine Chemical compound O=C1N=C(N)C=CN1[C@@H]1O[C@H](CO)CC1 WREGKURFCTUGRC-POYBYMJQSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YOEWQQVKRJEPAE-UHFFFAOYSA-L succinylcholine chloride (anhydrous) Chemical class [Cl-].[Cl-].C[N+](C)(C)CCOC(=O)CCC(=O)OCC[N+](C)(C)C YOEWQQVKRJEPAE-UHFFFAOYSA-L 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to polyisobutene base thermoplastic elastomer fields, more particularly to a kind of side group functionalized polyisobutylene base thermoplastic elastomer and preparation method thereof, it is reacted this method comprises: the isobutylene-based polymers of halogenation or halomethylation are contacted with nucleopilic reagent, the side group functionalized polyisobutylene base thermoplastic elastomer is made, the nucleopilic reagent is the nitrogenous compound that may participate in necleophilic reaction.Isobutenyl thermoplastic elastomer (TPE) of the invention forms polyisobutenyl physical cross-linked network by the multiple hydrogen bonding between functionalized side group, it assigns thermoplastic elastomer more excellent physical mechanical property, air-tightness and damping capacity, and makes it have excellent self-healing properties.
Description
Technical field
The invention belongs to polyisobutene base thermoplastic elastomer fields, different more particularly, to a kind of side group functionalized poly
Butylene base thermoplastic elastomer and preparation method thereof.
Background technique
Cation (co) polymerization, available isobutenyl polymerization are carried out by isobutene and other a small amount of multi-olefin monomers
Object.Due in isobutene structural unit on same carbon two substituent methyls presence, generate low diffusion coefficient and gas infiltration
Property, have excellent air-tightness and watertightness, and isobutylene-based polymers itself have excellent cryogenic property, tire,
Sealing material, insulating materials and Medical bottle stopper etc. have a wide range of applications, referring to Wu Guanying, Wu one string, " control sun from
Son polymerization and its application ", Beijing Chemical Industry Press, 2005,341-356.Polyisobutene or butyl rubber have nonpolarity
Feature leads to it with the poor adhesion of metal or rubber, needs to be modified butyl rubber.It is with halogenation modification butyl rubber
Example, after butyl rubber passes through halogenation, except the air-tightness and watertightness of reservation butyl rubber, damping, resistance to ozone, chemically-resistant are situated between
Outside matter and cryogenic property, butyl rubber polarity and rate of cure also can be improved, improve the compatibility with natural rubber, butadiene-styrene rubber
And bond properties, referring to patent CN201110266048.But chemical bond crosslinking is formed after halogenated butyl rubber vulcanization, cause
The not reproducible processing of butyl rubber after vulcanization, it is difficult to realize its recycling and reusing.
Thermoplastic elastomer (TPE) is the material for processing as plastics and be elastomer under a type high temp under room temperature, passes through molecule
Between active force form physics crosslinking points or cross-linked areas, physical crosslinking variation with temperature is in reversible change, makes thermoplastic elastic
Body has the characteristic for repeating processing and recycling and reusing, is known as green rubber.It can not be into make up conventional vulcanization butyl rubber
Row repeats the defect of processed and applied, by the modification to isobutylene-based polymers, reversible crosslink is formed in molecule interchain, thus both
It is able to maintain conventional vulcanized rubbers physical property, and can be carried out plasticity and repeat processed and applied.In the prior art, by the way that cyclopentadiene will be contained
(CPD) the organoaluminium compound [(CH of base3)2AlCPD] it is reacted with chlorinated scoline, the chlorination fourth with CPD side group is made
Base rubber has thermal reversion conversion behavior, referring to Kennedy J P, Castncr K F.Thermally reversible
polymer systems by cyclopentadienylation.Ⅱ.The synthesis of cyclopentadiene-
Containing polymer, Journal of Polymer Science, Polymer Chemistry Edition, 1979,
17(7):2055-2070；Using cyclopentadiene at normal temperature automatic dimerization at dicyclopentadiene (DCPD) and DCPD at high temperature
It can be depolymerized to the reversible Diels-Alder reaction of cyclopentadiene again, the derivative of CPD or DCPD is introduced into isobutylene-based polymers
In, reversible crosslink structure is formed by dynamic covalent bond, generates thermoplastic elastomer (TPE), referring to Wagener K B, Engle L P,
Thermally reversible polymer linkages covalently cross-linked poly
(azlactone), Macromolecules, 1991,24 (26): 6809-6815.
It is extremely important for forming reversible crosslink structure by hydrogen bond.By carrying out chemical modification to isobutylene-based polymers
Hydrogen bond crosslinks isobutylene-based elastomer can be prepared.It is reacted using large excess of 4- semicarbazides pyrimidine with brombutyl,
Though the butyl rubber of thermal reversion crosslinking can be prepared, need in the reaction system using toluene solvant and a large amount of consisting of phase-transferring agent,
And reaction efficiency is low, when 4- semicarbazides pyrimidine dosage is 1 molar equivalent, reaction efficiency only has 35%, when 4- semicarbazides pyrimidine
When more than dosage excessive 5 molar equivalents, reaction efficiency also only has 60%, when 4- semicarbazides pyrimidine dosage is in 10~20 molar equivalents
Under, reaction efficiency also can only achieve 70%, and excessive 4- semicarbazides pyrimidine and consisting of phase-transferring agent remain, and cause reaction product purification tired
Difficulty influences performance, and toluene solvant is not environmentally.Referring to: Bai Huarong, Cheng Bin, 4- semicarbazides pyrimidine are reacted with brombutyl
Prepare thermal reversion crosslinked butyl rubber, China Synthetic Rubber Industry, 2008,31 (3): 195-199.By end group allyl chloride functionalized poly
Isobutenyl is reacted with thymidine, forms polyisobutene cross-linked network, but system reaction effect by terminal functionality hydrogen bond
Rate is also low, obtained product hydrogen bond crosslinks effect relative mistake.Referring to: Ojha U., Rajkhowa R., Agnihotra S.R.,
Faust R.A new general methodology for the syntheses of end-functional
Polyisobutylenes by nucleophilic substitution reactions, Macromolecules, 2013,
41(11):3832-3841.Using click chemistry method, the modified thymidine of azido group is reacted with halogenated butyl rubber, though
Can be improved reaction efficiency, but due between main chain and thymidine containing between a 6C alkane chain and a five-ring heterocycles structure
Every group, the hydrogen bond action of generation farther out, influences the performance of material apart from main chain, referring to: Herbst F., Seiffert S.,
Binder W.H.,Dynamic supramolecular poly(isobutylene)s for self-healing
materials,Polymer Chemistry,2012,3:3084-3092。
Summary of the invention
The object of the present invention is to provide a kind of side group functionalized polyisobutylene base thermoplastic elastomers and preparation method thereof, should
Isobutenyl thermoplastic elastomer (TPE) forms polyisobutenyl by the multiple hydrogen bonding between the functionalized side group and is physical crosslinking net
Network can assign the excellent mechanical property of thermoplastic elastomer, damping capacity, air-tightness and self-healing properties without chemical crosslinking.
Specifically, the first aspect of the present invention provides a kind of side group functionalized polyisobutylene base thermoplastic elastomer, special
Sign is that the side group functionalized polyisobutylene base thermoplastic elastomer includes shown in structural unit and Formula II shown in Formulas I
Structural unit shown in structural unit and/or formula III；
In Formula II, R1、R2、R3It is each independently H, C1-C6Alkyl, Y be nitrogenous compound group；
In formula III, Y is nitrogenous compound group.
In accordance with the present invention it is preferred that nitrogenous compound group Y is the base of substituted or unsubstituted imidazole ring-containing feature structure
The group of group, the group of the feature structure containing pyrimidine ring, the group of the feature structure containing triazine ring or purine-containing feature structure.
Specifically, the group of the imidazole ring-containing feature structure is preferably selected from 2-methylimidazole, 4-methylimidazole, 1,2- bis-
Methylimidazole, 2,4- methylimidazole, 1- vinyl imidazole, 1- butylimidazolium, N- ethyl imidazol(e), N- propyl imidazole, 2- ten
One alkyl imidazole, 4,5- diphenyl-imidazole, trityl imidazole, chlorination 1- octyl -3- methylimidazole, chlorination 1- allyl -3-
The bromo- 4- nitroimidazole of methylimidazole, 2-, 4- nitroimidazole, the chloro- 4- nitroimidazole of 2-, 4- iodine imidazoles, the iodo- 1H- imidazoles of 4-, 2,
4,5- triiodo imidazoles, the iodo- 1H- imidazoles of 4,5- bis-, iodate 1- ethyl-3-methylimidazole, 2- sulfydryl -1- methylimidazole, 1- (4- nitre
Base benzyl) imidazoles, 1- (4- nitrobenzene) -1H- imidazoles, 1- (4- aminophenyl) imidazoles, 1- (4- aminobenzyl) imidazoles, 1- (2,
4,6- triisopropyl phenyl sulphonyl) imidazoles, 1- (4- carboxaldehyde radicals phenyl) imidazoles, N- acetyl imidazole, benzimidazole, 2- mercapto
Tolimidazole, 2,5,6- trimethyl benzimidazole, 2- (trifluoromethyl) benzimidazole, 2- hydroxybenzimidazole and 4- azepine
Group after the dehydrogenation of at least one of benzimidazole.
The group of the feature structure containing pyrimidine ring be preferably selected from including cytimidine, 5- azepine cytimidine, 6- chlorine cytimidine,
5- azepine cytimidine, 5- methyl -2'- methoxy ethoxy cytimidine, cytidine, 2,2'- ring cytidine, 2,3- are bis-
Deoxycytidine, 2'- desoxycytidine monohydrate, nucleosides -5- triphosphoric acid methylamino cytimidine, uracil, 6-
Formoxyl uracil, 5- acetyl group uracil, 2- methoxyl group -5 FU 5 fluorouracil, 5- (trifluoromethyl) uracil, 6- (fluoroform
Base) uracil, 2- ethyoxyl -5 FU 5 fluorouracil, 6- chlorouracil, the chloro- 3- methyluracil 5-bromouracil of 6-, 5- ioduria be phonetic
Pyridine, the bromo- 6- azauracil of 5-, 4- thiouracil, 6- phenyl -2- thiouracil, 5- ethoxycarbonyl -2- paper substrate and 5,6- bis-
Group after the dehydrogenation of at least one of amino -1- methyluracil.
The group of the triazine ring feature structure is preferably selected from melamine, trimethoxy trinitro- triazine, 2- nitre imines
Base -5- nitro-hexahydro -1,3,5- triazine, three-(Aminotetrazole) triazines, 4- aminoquinoline -1,3,5- triazine, hemel,
Group after the dehydrogenation of at least one of 2- amino -4- morpholine -1,3,5- triazine and methylol pentamethylmelamine.
It is de- that the group of the purine ring feature structure is preferably selected from least one of guanine, xanthine and hypoxanthine
Group after hydrogen.
In thermoplastic elastomer (TPE) of the invention, on the basis of the total mole number of structural unit in thermoplastic elastomer (TPE), Formulas I institute
The molar content for showing structural unit is 90% or more.I.e. main chain mainly contain 90mol% or more isobutene structural unit and
10mol% or less comonomer structural unit, side group are nitrogen-containing functional group, and degree of functionality 10mol% is hereinafter, it is preferred that 5% hereinafter, more
It is preferred that 2% or less.
In the present invention, C1-C6Alkyl include but is not limited to: methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, penta
Base, isopentyl, neopentyl.
To achieve the goals above, the present invention also provides a kind of systems of side group functionalized polyisobutylene base thermoplastic elastomer
Preparation Method reacts this method comprises: the isobutylene-based polymers of halogenation or halomethylation are contacted with nucleopilic reagent, is made
The side group functionalized polyisobutylene base thermoplastic elastomer, the nucleopilic reagent are the nitrogenous chemical combination that may participate in necleophilic reaction
Object, the preferably nitrogenous compound containing the lone pair electrons that may participate in nucleophilic substitution.
According to the present invention, it is that isobutenyl well known to those skilled in the art is poly- that the isobutylene-based polymers, which can be various,
Object is closed, concretely the copolymer of isobutene and at least one multi-olefin monomer and/or other copolymerisable monomers." other
Copolymerisable monomer " refers in addition to multi-olefin monomer, the monomer that can be closed with isobutylene copolymers.
In accordance with the present invention it is preferred that the multi-olefin monomer is C4-C14Multi-olefin monomer；Preferably isoprene, fourth
Diene, 2,4- dimethyl butadiene, 1,3- pentadiene, 3- methyl-1,3-pentylene, 2,4- hexadiene, 2- neopentyl butadiene,
At least one of cyclopentadiene, methyl cyclopentadiene and cyclohexadiene；Conjugated diene further preferably therein, it is optimal
It is selected as isoprene, butadiene, 1,3- pentadiene.
In accordance with the present invention it is preferred that other described copolymerisable monomers are that styrene or alkyl-substituted aromatic vinyl are total
Polycondensation monomer, preferably styrene or C1-C4Alkyl-substituted styrene, more preferably styrene or p-methylstyrene.
In accordance with the present invention it is preferred that the molar content of isobutene structural unit is 90% or more in the copolymer.
In accordance with the present invention it is preferred that the nucleopilic reagent is selected from glyoxaline compound, pyrimidines, triazines
Close at least one of object and purine compound；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, 4-methylimidazole, 1,2- methylimidazole, 2,4-
Methylimidazole, 1- vinyl imidazole, 1- butylimidazolium, N- ethyl imidazol(e), N- propyl imidazole, 2- undecyl imidazole, 4,
5- diphenyl-imidazole, trityl imidazole, chlorination 1- octyl -3- methylimidazole, chlorination 1- allyl -3- methylimidazole, 2- are bromo-
The chloro- 4- nitroimidazole of 4- nitroimidazole, 4- nitroimidazole, 2-, 4- iodine imidazoles, the iodo- 1H- imidazoles of 4-, 2,4,5- triiodo imidazoles, 4,
The iodo- 1H- imidazoles of 5- bis-, iodate 1- ethyl-3-methylimidazole, 2- sulfydryl -1- methylimidazole, 1- (4- nitrobenzyl) imidazoles, 1-
(4- nitrobenzene) -1H- imidazoles, 1- (4- aminophenyl) imidazoles, 1- (4- aminobenzyl) imidazoles, 1- (2,4,6- triisopropylbenzene
Base sulphonyl) imidazoles, 1- (4- carboxaldehyde radicals phenyl) imidazoles, N- acetyl imidazole, benzimidazole, 2- mercaptan ylmethylbenzimidazole,
In 2,5,6- trimethyl benzimidazole, 2- (trifluoromethyl) benzimidazole, 2- hydroxybenzimidazole and 4- azabenzimidazoles
It is at least one.
Preferably, pyrimidines are selected from phonetic including cytimidine, 5- azepine cytimidine, 6- chlorine cytimidine, 5- azepine born of the same parents
Pyridine, 5- methyl -2'- methoxy ethoxy cytimidine, cytidine, 2,2'- ring cytidine, 2,3- double deoxidation cytimidine
Nucleosides, 2'- desoxycytidine monohydrate, nucleosides -5- triphosphoric acid methylamino cytimidine, uracil, 6- formoxyl urine are phonetic
Pyridine, 5- acetyl group uracil, 2- methoxyl group -5 FU 5 fluorouracil, 5- (trifluoromethyl) uracil, 6- (trifluoromethyl) uracil,
The chloro- 3- methyluracil 5-bromouracil of 2- ethyoxyl -5 FU 5 fluorouracil, 6- chlorouracil, 6-, 5-iodouracil, the bromo- 6- of 5-
Azauracil, 4- thiouracil, 6- phenyl -2- thiouracil, 5- ethoxycarbonyl -2- paper substrate and 5,6- diaminostilbene-first
At least one of base uracil.
Preferably, the compound in triazine class is selected from melamine, trimethoxy trinitro- triazine, 2- nitre imido grpup -5-
Nitro-hexahydro -1,3,5- triazine, three-(Aminotetrazole) triazines, 4- aminoquinoline -1,3,5- triazine, hemel, 2- ammonia
At least one of base -4- morpholine -1,3,5- triazine and methylol pentamethylmelamine.
Preferably, the purine compound is selected from least one of guanine, xanthine and hypoxanthine.
Heretofore described " isobutylene-based polymers of halogenation or halomethylation " can be made by conventional method in that art
Or it is commercially available.The preparation method is for example: isobutylene-based polymers are reacted with bromine.
According to the present invention, relative to the halogen element in the isobutylene-based polymers of halogenation or halomethylation, the nucleophilic examination
The dosage of agent is preferably 0.05~1.0 molar equivalent, further preferred 0.1~1.0 molar equivalent, and more preferable 0.2~1.0 mole
Equivalent.By adjust isobutylene-based polymers in halogen element and its with the molar equivalent ratio of nucleopilic reagent, adjustable isobutene
Nitrogenous side group degree of functionalization in based polyalcohol.
The isobutylene-based polymers and the nucleophilic substitution technique of nucleopilic reagent may include solwution method and fusion method, with
And other equivalent reaction methods well known by persons skilled in the art.
According to an embodiment of the present invention, the reaction is solwution method, and the isobutenyl of halogenation or halomethylation is gathered
Close object, nucleopilic reagent is reacted at least one organic solvent exposure.The organic solvent is preferably alkane, tetrahydrofuran or chlorination
Hydrocarbon.The condition of the solwution method preferably includes: reaction temperature be 10~150 DEG C, preferably 15~100 DEG C, more preferable 20~100
℃；Reaction time is 2~40h, preferably 5~25h, more preferable 8~22h.Reaction temperature has with the solvent and its boiling point being selected from
It closes, the reaction time again relies on reaction temperature, and in the case where reaching same reaction efficiency, reaction temperature is high, then needs the time
It is short.
Another embodiment according to the present invention, the reaction is solid phase/fusion method, by halogenation or the isobutyl of halomethylation
Alkenyl polymer and nucleopilic reagent carry out haptoreaction, for example, carried out after being pre-mixed extrusion reaction or in vulcanizing press it is anti-
It should form, perhaps hybrid reaction in situ or the hybrid reaction in situ in open mill or mixer in an extruder.It is described solid
Phase/fusion method condition include: reaction temperature be 90~170 DEG C, preferably 95~150 DEG C, more preferable 100~150 DEG C, this with it is anti-
Answer the boiling point of object related；Reaction time is 1~300min, preferably 2~200min, more preferable 3~130min.Reaction time relies on
In reaction temperature, in the case where reaching same reaction efficiency, reaction temperature is high, then needs the time short.
The second aspect of the present invention provides the side group functionalized polyisobutylene based thermoplastic bullet as made from above-mentioned preparation method
Property body.
The advantages and effects of the present invention are: functionalized polyisobutylene based thermoplastic obtained is elastic by the method for the invention
Body, reaction efficiency is high, and the physical mechanical property and dynamic mechanical of product are promoted obviously, has more excellent damping capacity
And air-tightness, repeatable processability and excellent self-healing properties with thermoplastic elastomer (TPE).Preparation process of the invention
Simply, reaction efficiency is high, easily operated, has potential application.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.
Analysis method of the present invention is as follows:
Utilize the storage modulus G ', loss modulus G " and damage of TA-Q800 dynamic thermomechanical analysis apparatus (DMA) test material
Consume angle tangent tan δ.
According to GB/T1040-1BA, the elongation at break ε and tensile strength Ts of universal testing machine characterization material are utilized.
According to GB1038-2000, the oxygen transmission coefficient OTR of VAC-V2 pressure differential gas permeameter test material is utilized.
Using the variation of optical microphotograph sem observation sample surfaces scratch, record changes with time situation with scratch length.
Embodiment 1
(1) 50g isobutene-p-methylstyrene copolymer IMS (benzyl content 1.33mol%) is dissolved in 500mL hexane,
0.1g azobisisoheptonitrile is added, adds 2.5mL bromine, reacts 50min at 65 DEG C, suitable KOH aqueous solution is added, eventually
Only react.By glue precipitating in ethanol, brominated isobutylene-p-methylstyrene copolymer (BIMS) is obtained, in 40 DEG C of baking ovens
Middle drying obtains dry brominated isobutylene-p-methylstyrene copolymer BIMS, and wherein bromine content is 0.6mol%.
(2) take the above-mentioned brominated isobutylene of 10g-p-methylstyrene copolymer BIMS and 170mg butyl imidazole at 40 DEG C
Mixing, wherein relative to bromo functional groups, the molar equivalent of butyl imidazole is 1.0.
(3) the irriidazole-functionalized isobutyl of side group is prepared in 110 DEG C of reactions 10min, revolving speed 100rpm in said mixture
Alkene-p-methylstyrene copolymer thermoplastic elastomer (IIMS), wherein nitrogen-containing functional group molar content is 0.57mol%, instead
Efficiency is answered to reach 95%.
The tensile strength (Ts) of prepared IIMS thermoplastic elastomer is 3.05MPa, and elongation at break ε is 301%；With it is right
Ratio 1 (butyl rubber IIR) is compared, and Ts improves 180%, and elongation at break variation is little；With 2 (butyl rubber bromide of comparative example
Glue BIIR is chemically crosslinked vulcanizate BIIR-S) it compares, mechanical property is suitable.
The air-tightness of prepared IIMS thermoplastic elastomer is excellent, and air transmission coefficient is only 2.23 × 10-14cm3·cm/cm2·
s·Pa；Compared with comparative example 1 (butyl rubber BIIR), air-tightness improves 311%；With 2 (brombutyl of comparative example
BIIR is chemically crosslinked vulcanizate BIIR-S) it compares, air-tightness improves 203%.
Storage modulus G ' of the prepared IIMS thermoplastic elastomer at 25 DEG C is 0.99MPa, and loss modulus G " is
0.21MPa, tan δ be 0.31, at -20 DEG C, tan δ reaches maximum value 1.72, the temperature range as tan δ > 0.3 be -66~
20 DEG C, temperature difference is 86 DEG C, has widened damping capacity temperature range range, has further increased damping capacity；With (the butyl rubber of comparative example 1
Glue IIR) compare, the G ' at 25 DEG C improves 28%, and G " improves the maximum value raising that 62%, tan δ improves 35%, tan δ
The temperature range of δ > 0.3 16%, tan widens 8 DEG C, and damping capacity improves；With (the brombutyl BIIR chemistry of comparative example 2
Cross-linking vulcanized glue BIIR-S) compare, the maximum value that the tan δ at 25 DEG C improves 10%, tan δ improves 20%, other performances
Quite, damping capacity improves.
IIMS sample has excellent self-healing properties, is about 395 μm of scratch under room temperature in the case where sample surfaces are drawn, stands
Selfreparing reaches 85% after 5h；Comparative example 1 (butyl rubber BIIR) is compared, and the selfreparing degree of BIIR-S5h improves 572%；
Brombutyl BIIR is chemically crosslinked vulcanizate BIIR-S in comparative example 2, still without reviewing one's lessons by oneself recurrent images after 5h.
Embodiment 2
(1) it by the sodium ethoxide of 10g brombutyl (BIIR), 270mg guanine (G) and 228mg, is dissolved at 40 DEG C
Mixing, wherein guanine molar equivalent is 0.95.
(2) said mixture reacts 20min at 130 DEG C, and thermoplastic elastomer (TPE) is prepared in revolving speed 100rpm
(GIIR), wherein guanine functional group molar content is 0.98mol%, and reaction efficiency reaches 97%.
The tensile strength Ts of GIIR sample is 3.03MPa, and elongation at break ε is 509%；With 1 (butyl rubber of comparative example
BIIR it) compares, Ts improves 175%, and elongation at break variation is little；With comparative example 2 (brombutyl BIIR vulcanizate)
It compares, mechanical property is suitable.
The air-tightness of GIIR sample is excellent, and air transmission coefficient is 2.28 × 10-14cm3·cm/cm2·s·Pa；With comparative example 1
(butyl rubber BIIR) is compared, and air-tightness improves 302%；(brombutyl BIIR is chemically crosslinked vulcanizate with comparative example 2
BIIR-S it) compares, air-tightness improves 200%.
Storage modulus G ' of the GIIR sample at 25 DEG C is 1.2MPa, and loss modulus G " is 0.31MPa, and tan δ is 0.26,
At -24 DEG C, tan δ reaches maximum value 1.55, and temperature range when tan δ > 0.3 is -57~23 DEG C, and temperature difference is 80 DEG C, is widened
Damping capacity temperature range range, further increases damping capacity；Compared with comparative example 1 (butyl rubber IIR), the G ' at 25 DEG C is mentioned
High by 56%, G " improves 138%, tan δ and improves %, and the maximum value of tan δ improves the temperature range of δ > 0.3 5%, tan
Mobile to room temperature direction, damping capacity improves；With comparative example 2 (brombutyl BIIR is chemically crosslinked vulcanizate BIIR-S) ratio
Compared with the tan δ at 25 DEG C improves 10%, and damping capacity improves, other performances are suitable.
GIIR sample has excellent self-healing properties, is about 540 μm of scratch under room temperature in the case where sample surfaces are drawn, stands
Selfreparing reaches 80% after 4h.
Embodiment 3
(1) 10g brombutyl BIIR, 225mg melamine (M), 228mg sodium ethoxide and 100mL THF are dissolved
Mixing, melamine molar equivalent are 0.95.
(2) thermoplastic elastomer (TPE) is prepared in 120 DEG C of reactions 10min, revolving speed 100rpm by said mixture
(MIIR), wherein melamine functional group molar content is 0.99mol%, and reaction efficiency reaches 98%.
The tensile strength Ts of MIIR sample is 3.73MPa, and elongation at break ε is 511%；With 1 (butyl rubber of comparative example
BIIR it) compares, Ts improves 239%, and elongation at break variation is little；With comparative example 2 (brombutyl BIIR vulcanizate)
It compares, mechanical property is suitable.
The air-tightness of MIIR sample is excellent, and air transmission coefficient is 2.17 × 10-14cm3·cm/cm2·s·Pa；With comparative example 1
(butyl rubber BIIR) is compared, and air-tightness improves 323%；(brombutyl BIIR is chemically crosslinked vulcanizate with comparative example 2
BIIR-S it) compares, air-tightness improves 210%.
Storage modulus G ' of the MIIR sample at 25 DEG C is 1.10MPa, and loss modulus G " is 0.39MPa, and tan δ is 0.35,
At -20 DEG C, tan δ reaches maximum value 1.56, and temperature range when tan δ > 0.3 is -51~28 DEG C, and temperature difference is 79 DEG C, into one
Step improves damping capacity；Compared with comparative example 1 (butyl rubber IIR), the G ' at 25 DEG C improves 43%, and G " improves 200%,
The temperature range that the maximum value that tan δ improves 106%, tan δ improves δ > 0.3 11%, tan is mobile to room temperature direction, damping
Performance improves；Compared with comparative example 2 (brombutyl BIIR is chemically crosslinked vulcanizate BIIR-S), the tan δ at 25 DEG C is improved
The maximum value of 20%, tan δ improves 10%, and damping capacity improves, other performances are suitable.
MIIR sample has excellent self-healing properties, is about 440 μm of scratch under room temperature in the case where sample surfaces are drawn, stands
Selfreparing reaches 80% after 3.5h.
Embodiment 4
(1) by the sodium ethoxide of 10g brombutyl BIIR, 215mg uracil (U) and 228mg, (uracil mole is worked as
Amount is 1.0), to mix at 40 DEG C in 100ml THF.
(2) thermoplastic elastomer (TPE) is prepared in 130 DEG C of reactions 20min, revolving speed 100rpm by said mixture
(UIIR), wherein guanine functional group molar content is 1.02mol%, reaction efficiency 95%.
The tensile strength Ts of UIIR sample is 4.13MPa, and elongation at break ε is 517%；With 1 (butyl rubber of comparative example
BIIR it) compares, Ts improves 275%, and elongation at break variation is little；With comparative example 2 (brombutyl BIIR vulcanizate)
It compares, mechanical property is suitable.
The air-tightness of UIIR sample is excellent, and air transmission coefficient is 2.14 × 10-14cm3·cm/cm2·s·Pa；With comparative example 1
(butyl rubber BIIR) is compared, and air-tightness improves 329%；(brombutyl BIIR is chemically crosslinked vulcanizate with comparative example 2
BIIR-S it) compares, air-tightness improves 220%.
Storage modulus G ' of the UIIR sample at 25 DEG C is 1.1MPa, and loss modulus G " is 0.36MPa, and tan δ is 0.33,
At -22 DEG C, tan δ reaches maximum value 1.58, and temperature range when tan δ > 0.3 is -56~27 DEG C, and temperature difference is 83 DEG C, is widened
Damping capacity temperature range range, further increases damping capacity；Compared with comparative example 1 (butyl rubber IIR), the G ' at 25 DEG C is mentioned
High by 43%, G ", which improves 177%, tan δ and improves the maximum value of 154%, tan δ, improves the temperature of δ > 0.3 13%, tan
Range is widened from -60~18 DEG C to -56~27 DEG C, is provided with good damping capacity under room temperature, is also improved integral damping
Energy；Compared with comparative example 2 (brombutyl BIIR is chemically crosslinked vulcanizate BIIR-S), the tan δ at 25 DEG C is improved
The maximum temperature that the maximum value of 10%, tan δ improve δ=0.3 20%, tan is increased to 27 DEG C from 25 DEG C, and damping capacity improves.
UIIR sample has excellent self-healing properties, is about 355 μm of scratch under room temperature in the case where sample surfaces are drawn, stands
Selfreparing reaches 80% after 3.5h.
Embodiment 5
10g brombutyl BIIR, 215mg uracil (U), 228mg sodium ethoxide are mixed with 100ml THF and (urinated phonetic
Pyridine molar equivalent is 1.0), to react 20h at 50 DEG C in solution, removes solvent and catalyst, obtains thermoplasticity after cleaning-drying
Elastomer UIIR-2, wherein hydrogen bond functional groups' molar content is 0.79mol%, reaction efficiency 74%.
The tensile strength Ts of UIIR-2 sample is 2.4MPa, and elongation at break ε is 400%；With 1 (butyl rubber of comparative example
BIIR it) compares, Ts improves 118%, and elongation at break variation is little；(brombutyl BIIR is chemically crosslinked with comparative example 2
Vulcanizate BIIR-S) it compares, mechanical property is suitable.
The air-tightness of UIIR-2 sample is excellent, and air transmission coefficient is 2.31 × 10-14cm3·cm/cm2·s·Pa；With comparative example
1 (butyl rubber BIIR) is compared, and air-tightness improves 297%；(brombutyl BIIR chemical crosslinking vulcanizes with comparative example 2
Glue BIIR-S) it compares, air-tightness improves 190%.
Storage modulus G ' of the UIIR-2 sample at 25 DEG C is 0.8MPa, and loss modulus G " is 0.22MPa, and tan δ is
0.27, at -23 DEG C, tan δ reaches maximum value 1.52, and temperature range when tan δ > 0.3 is -55~23 DEG C, further increases resistance
Damping properties；Compared with comparative example 1 (butyl rubber IIR), the G ' at 25 DEG C improves 3%, and G " improves 69%, tan δ and improves
Temperature when 59%, tan δ reach maximum value is suitable, and the maximum value of tan δ improves the temperature range of δ > 0.3 3%, tan to room
Warm direction is mobile, and damping capacity improves；Compared with comparative example 2 (brombutyl BIIR is chemically crosslinked vulcanizate BIIR-S),
The maximum value of tan δ improves 10%, other performances are suitable, and damping capacity improves.
UIIR-2 sample has excellent self-healing properties, is about 520 μm of scratch under room temperature in the case where sample surfaces are drawn, quiet
Selfreparing reaches 80% after setting 4.5h.
Embodiment 6
(1) by the sodium ethoxide of 10g brombutyl BIIR, 140mg guanine (G) and 114mg, (guanine mole is worked as
Amount is 0.5), to mix at 40 DEG C.
(2) thermoplastic elastomer (TPE) (GIIR- is prepared by said mixture 20min at 130 DEG C, revolving speed 100rpm
2), wherein guanine functional group molar content is 0.51mol%, and reaction efficiency reaches 96%.
The tensile strength Ts of GIIR-2 sample is 2.14MPa, and elongation at break ε is 244%；With 1 (butyl rubber of comparative example
BIIR it) compares, Ts improves 95%；Compared with comparative example 2 (brombutyl BIIR vulcanizate), mechanical property is suitable.
The air transmission coefficient of GIIR-2 sample is 4.01 × 10-14cm3·cm/cm2SPa, air-tightness are excellent；With comparative example
1 (butyl rubber BIIR) is compared, and air-tightness improves 130%；(brombutyl BIIR chemical crosslinking vulcanizes with comparative example 2
Glue BIIR-S) it compares, air-tightness improves 69%.
Storage modulus G ' of the GIIR-2 sample at 25 DEG C is 0.98MPa, and loss modulus G " is 0.20MPa, and tan δ is
0.20, at -23 DEG C, tan δ reaches maximum value 1.48, and temperature range when tan δ > 0.3 is -60~19 DEG C, and temperature difference is 79 DEG C；
Compared with comparative example 1 (butyl rubber IIR), the G ' at 25 DEG C improves 27%, and G " improves 53%, tan δ and improves 18%,
The maximum value of tan δ is suitable, and the temperature range of δ > 0.3 tan is widened, and damping capacity improves；With 2 (butyl rubber bromide of comparative example
Glue BIIR is chemically crosslinked vulcanizate BIIR-S) compare, tan δ maximum value improves 8%, other performances are suitable, and damping capacity mentions
It is high.
GIIR-2 sample has excellent self-healing properties, is about 510 μm of scratch under room temperature in the case where sample surfaces are drawn, quiet
Selfreparing reaches 80% after setting 6.5h.
Comparative example 1
The Ts of butyl rubber IIR is 1.1MPa, ε 600%；G ' at 25 DEG C is 0.77MPa, and G " is 0.13MPa,
Tan δ is 0.17, reaches maximum value 1.48 in -20 DEG C of tan δ, the temperature range of δ > 0.3 tan is -60~18 DEG C；Air transmission coefficient is
9.17×10-14cm3·cm/cm2·s·Pa；430 μm of scratch is about under room temperature in the case where sample surfaces are drawn, is stood, scratch is contracting
It is short to after 380 μm and just no longer changes, selfreparing degree is 12%.
Comparative example 2
(1) it by 10g brombutyl BIIR and 0.5g sulphur, is placed in two-roll mill, revolving speed 40r/min, is kneaded
40 DEG C of temperature, it is kneaded 10min.
(2) sizing material after mixing is placed in compression molding instrument, curing temperature is 160 DEG C, vulcanization time 45min, system
The standby brombutyl BIIR-S vulcanized.
The state of cure (vulcanization) of BIIR-S is 1%, Ts 3.8MPa, ε 640%；G ' at 25 DEG C is 1.9MPa, and G " is
0.57MPa, tan δ are 0.30, reach maximum value 1.37 in -22 DEG C of tan δ, the temperature range of δ > 0.3 tan is -59~25 DEG C；Thoroughly
Gas coefficient is 6.76 × 10-14cm3·cm/cm2·s·Pa；645 μm of scratch is about under room temperature in the case where sample surfaces are drawn, is stood,
Substantially recurrent images are not reviewed one's lessons by oneself.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of side group functionalized polyisobutylene base thermoplastic elastomer, which is characterized in that the side group functionalized polyisobutylene base
Thermoplastic elastomer (TPE) includes structure shown in structural unit shown in structural unit and Formula II shown in Formulas I and/or formula III
Unit；
In Formula II, R1、R2、R3It is each independently H, C1-C6Alkyl, Y be nitrogenous compound group；
In formula III, Y is nitrogenous compound group；
Preferably, nitrogenous compound group Y is the group of substituted or unsubstituted imidazole ring-containing feature structure, feature containing pyrimidine ring
The group of the group of structure, the group of the feature structure containing triazine ring or purine-containing feature structure；
It is further preferred that the group of the imidazole ring-containing feature structure is selected from 2-methylimidazole, 4-methylimidazole, 1,2- diformazan
Base imidazoles, 2,4- methylimidazole, 1- vinyl imidazole, 1- butylimidazolium, N- ethyl imidazol(e), N- propyl imidazole, 2- 11
Alkyl imidazole, 4,5- diphenyl-imidazole, trityl imidazole, chlorination 1- octyl -3- methylimidazole, chlorination 1- allyl -3- first
The bromo- 4- nitroimidazole of base imidazoles, 2-, 4- nitroimidazole, the chloro- 4- nitroimidazole of 2-, 4- iodine imidazoles, the iodo- 1H- imidazoles of 4-, 2,4,
5- triiodo imidazoles, the iodo- 1H- imidazoles of 4,5- bis-, iodate 1- ethyl-3-methylimidazole, 2- sulfydryl -1- methylimidazole, 1- (4- nitro
Benzyl) imidazoles, 1- (4- nitrobenzene) -1H- imidazoles, 1- (4- aminophenyl) imidazoles, 1- (4- aminobenzyl) imidazoles, 1- (2,4,
6- triisopropyl phenyl sulphonyl) imidazoles, 1- (4- carboxaldehyde radicals phenyl) imidazoles, N- acetyl imidazole, benzimidazole, 2- mercapto first
Base benzimidazole, 2,5,6- trimethyl benzimidazole, 2- (trifluoromethyl) benzimidazole, 2- hydroxybenzimidazole and 4- pyridine
And the group after the dehydrogenation of at least one of imidazoles；
It includes cytimidine, 5- azepine cytimidine, 6- chlorine cytimidine, 5- azepine born of the same parents that the group of the feature structure containing pyrimidine ring, which is selected from,
Pyrimidine, 5- methyl -2'- methoxy ethoxy cytimidine, cytidine, 2,2'- ring cytidine, 2,3- double deoxidation born of the same parents are phonetic
Pyridine nucleosides, 2'- desoxycytidine monohydrate, nucleosides -5- triphosphoric acid methylamino cytimidine, uracil, 6- formoxyl urine
Pyrimidine, 5- acetyl group uracil, 2- methoxyl group -5 FU 5 fluorouracil, 5- (trifluoromethyl) uracil, 6- (trifluoromethyl) urine are phonetic
Pyridine, 2- ethyoxyl -5 FU 5 fluorouracil, 6- chlorouracil, the chloro- 3- methyluracil 5-bromouracil of 6-, 5-iodouracil, 5-
Bromo- 6- azauracil, 4- thiouracil, 6- phenyl -2- thiouracil, 5- ethoxycarbonyl -2- paper substrate and 5,6- diamino -
Group after the dehydrogenation of at least one of 1- methyluracil；
The group of the triazine ring feature structure is selected from melamine, trimethoxy trinitro- triazine, 2- nitre imido grpup -5- nitre
Base-hexahydro -1,3,5- triazine, three-(Aminotetrazole) triazines, 4- aminoquinoline -1,3,5- triazine, hemel, 2- amino -
Group after the dehydrogenation of at least one of 4- morpholine -1,3,5- triazine and methylol pentamethylmelamine；
The group of the purine ring feature structure is selected from the base after the dehydrogenation of at least one of guanine, xanthine and hypoxanthine
Group.
2. side group functionalized polyisobutylene base thermoplastic elastomer according to claim 1, wherein with thermoplastic elastomer (TPE)
On the basis of the total mole number of middle structural unit, the molar content of structural unit shown in Formulas I is 90% or more.
3. a kind of preparation method of side group functionalized polyisobutylene base thermoplastic elastomer, which is characterized in that this method comprises: will
The isobutylene-based polymers of halogenation or halomethylation are contacted with nucleopilic reagent is reacted, and the side group functionalized poly isobutyl is made
Alkenyl thermoplastic elastomer (TPE), the nucleopilic reagent are the nitrogenous compound that may participate in necleophilic reaction.
4. preparation method according to claim 1, wherein the isobutylene-based polymers are that isobutene and at least one are more
The copolymer of olefinic monomer and/or other copolymerisable monomers.
5. the preparation method according to claim 4, wherein the multi-olefin monomer is C4-C14Multi-olefin monomer；It is preferred that
For isoprene, butadiene, 2,4- dimethyl butadiene, 1,3- pentadiene, 3- methyl-1,3-pentylene, 2,4- hexadiene, 2-
At least one of neopentyl butadiene, cyclopentadiene, methyl cyclopentadiene and cyclohexadiene, further preferably isoamyl two
Alkene, butadiene, 1,3- pentadiene；Other described copolymerisable monomers be styrene, alkyl-substituted vinyl aromatic comonomer,
Preferably styrene or C1-C4Alkyl-substituted styrene, more preferably styrene or p-methylstyrene.
6. preparation method according to claim 3, wherein the nucleopilic reagent is selected from glyoxaline compound, miazines
Close at least one of object, compound in triazine class and purine compound；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, 4-methylimidazole, 1,2- methylimidazole, 2,4- diformazan
Base imidazoles, 1- vinyl imidazole, 1- butylimidazolium, N- ethyl imidazol(e), N- propyl imidazole, 2- undecyl imidazole, 4,5- bis-
Phenylimidazole, trityl imidazole, chlorination 1- octyl -3- methylimidazole, chlorination 1- allyl -3- methylimidazole, the bromo- 4- nitre of 2-
The chloro- 4- nitroimidazole of base imidazoles, 4- nitroimidazole, 2-, 4- iodine imidazoles, the iodo- 1H- imidazoles of 4-, 2,4,5- triiodo imidazoles, 4,5- bis-
Iodo- 1H- imidazoles, iodate 1- ethyl-3-methylimidazole, 2- sulfydryl -1- methylimidazole, 1- (4- nitrobenzyl) imidazoles, 1- (4- nitre
Base benzene) -1H- imidazoles, 1- (4- aminophenyl) imidazoles, 1- (4- aminobenzyl) imidazoles, 1- (2,4,6- triisopropyl phenyl sulphur
Acyl) imidazoles, 1- (4- carboxaldehyde radicals phenyl) imidazoles, N- acetyl imidazole, benzimidazole, 2- mercaptan ylmethylbenzimidazole, 2,5,
In 6- trimethyl benzimidazole, 2- (trifluoromethyl) benzimidazole, 2- hydroxybenzimidazole and 4- azabenzimidazoles at least
It is a kind of；
It includes cytimidine, 5- azepine cytimidine, 6- chlorine cytimidine, 5- azepine cytimidine, 5- methyl-that pyrimidines, which are selected from,
2'- methoxy ethoxy cytimidine, cytidine, 2,2'- ring cytidine, 2,3- ddC, 2'- are de-
Oxygen cytidin monohydrate, nucleosides -5- triphosphoric acid methylamino cytimidine, uracil, 6- formoxyl uracil, 5- acetyl group
Uracil, 2- methoxyl group -5 FU 5 fluorouracil, 5- (trifluoromethyl) uracil, 6- (trifluoromethyl) uracil, 2- ethyoxyl -5-
The chloro- 3- methyluracil 5-bromouracil of fluorouracil, 6- chlorouracil, 6-, 5-iodouracil, the bromo- 6- azauracil of 5-, 4-
In thiouracil, 6- phenyl -2- thiouracil, 5- ethoxycarbonyl -2- paper substrate and 5,6- diaminostilbene-methyluracil
It is at least one；
The compound in triazine class is selected from melamine, trimethoxy trinitro- triazine, 2- nitre imido grpup -5- nitro-hexahydro -
1,3,5- triazine, three-(Aminotetrazole) triazines, 4- aminoquinoline -1,3,5- triazine, hemel, morpholine -1 2- amino -4-,
At least one of 3,5- triazine and methylol pentamethylmelamine；
The purine compound is selected from least one of guanine, xanthine and hypoxanthine.
7. preparation method according to claim 3, wherein relative in the isobutylene-based polymers of halogenation or halomethylation
Halogen element, the dosage of the nucleopilic reagent is 0.05~1.0 molar equivalent, further preferred 0.1~1.0 molar equivalent, more
It is preferred that 0.2~1.0 molar equivalent.
8. preparation method according to claim 3, wherein the reaction is solwution method, by the different of halogenation or halomethylation
Butylene based polyalcohol, nucleopilic reagent are reacted at least one organic solvent exposure；The organic solvent is preferably alkane, tetrahydro furan
It mutters or chlorinated hydrocabon；The condition of the solwution method preferably includes: reaction temperature be 10~150 DEG C, preferably 15~100 DEG C, more preferably
20~100 DEG C；Reaction time is 2~40h, preferably 5~25h, more preferable 8~22h.
9. preparation method according to claim 3, wherein the reaction is solid phase/fusion method, by halogenation or halomethylation
Isobutylene-based polymers and nucleopilic reagent carry out haptoreaction；The condition of the solid phase/fusion method includes: that reaction temperature is 90
~170 DEG C, preferably 95~150 DEG C, more preferable 100~150 DEG C；Reaction time be 1~300min, preferably 2~200min, it is more excellent
Select 3~130min.
10. side group functionalized polyisobutylene based thermoplastic bullet made from preparation method described in any one of claim 3-9
Property body.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105398291A (en) * | 2014-09-05 | 2016-03-16 | 固特异轮胎和橡胶公司 | Pneumatic Tire With Post Cure Sealant Layer |
| CN105669882A (en) * | 2014-11-18 | 2016-06-15 | 北京化工大学 | Azonium-ionized poly(styrene-b-isobutylene-b-styrene) triblock copolymer and preparation method thereof |
-
2018
- 2018-04-04 CN CN201810298752.9A patent/CN110343205A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105398291A (en) * | 2014-09-05 | 2016-03-16 | 固特异轮胎和橡胶公司 | Pneumatic Tire With Post Cure Sealant Layer |
| CN105669882A (en) * | 2014-11-18 | 2016-06-15 | 北京化工大学 | Azonium-ionized poly(styrene-b-isobutylene-b-styrene) triblock copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| J.S. PARENT ET AL.: "Imidazolium bromide derivatives of poly(isobutylene-co-isoprene): A new class of elastomeric ionomers", 《POLYMER》 * |
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