CN103965381B - 一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法 - Google Patents
一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法 Download PDFInfo
- Publication number
- CN103965381B CN103965381B CN201310042536.5A CN201310042536A CN103965381B CN 103965381 B CN103965381 B CN 103965381B CN 201310042536 A CN201310042536 A CN 201310042536A CN 103965381 B CN103965381 B CN 103965381B
- Authority
- CN
- China
- Prior art keywords
- mercaptan
- thioether
- ethyl
- alcohol
- butyl
- 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.)
- Active
Links
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 37
- 239000003999 initiator Substances 0.000 title claims abstract description 31
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 25
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 7
- 239000012442 inert solvent Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 68
- -1 alcohol compound Chemical group 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 150000003568 thioethers Chemical class 0.000 claims description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 15
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 13
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical group CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 10
- 150000002989 phenols Chemical group 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000003053 piperidines Chemical class 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 8
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 8
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 8
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 8
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003222 pyridines Chemical class 0.000 claims description 7
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 6
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 claims description 6
- YWHLKYXPLRWGSE-UHFFFAOYSA-N Dimethyl trisulfide Chemical compound CSSSC YWHLKYXPLRWGSE-UHFFFAOYSA-N 0.000 claims description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 4
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 claims description 4
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical class CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 claims description 4
- WAYNDWSLNIRTJK-UHFFFAOYSA-N 2,4-diethylpiperidine Chemical class CCC1CCNC(CC)C1 WAYNDWSLNIRTJK-UHFFFAOYSA-N 0.000 claims description 4
- QOZOFODNIBQPGN-UHFFFAOYSA-N 2,4-dimethylpiperidine Chemical compound CC1CCNC(C)C1 QOZOFODNIBQPGN-UHFFFAOYSA-N 0.000 claims description 4
- PPRWPCMILDCTGF-UHFFFAOYSA-N 2,6-diethylpiperidine Chemical class CCC1CCCC(CC)N1 PPRWPCMILDCTGF-UHFFFAOYSA-N 0.000 claims description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 4
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims description 4
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 claims description 4
- QBBKKFZGCDJDQK-UHFFFAOYSA-N 2-ethylpiperidine Chemical compound CCC1CCCCN1 QBBKKFZGCDJDQK-UHFFFAOYSA-N 0.000 claims description 4
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 claims description 4
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 claims description 4
- MFEIKQPHQINPRI-UHFFFAOYSA-N 3-Ethylpyridine Chemical compound CCC1=CC=CN=C1 MFEIKQPHQINPRI-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 4
- KWHPWBXOLZTZMJ-UHFFFAOYSA-N 4-ethylpiperidine Chemical compound CCC1CCNCC1 KWHPWBXOLZTZMJ-UHFFFAOYSA-N 0.000 claims description 4
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 claims description 4
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 4
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 229960000452 diethylstilbestrol Drugs 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZVEZMVFBMOOHAT-UHFFFAOYSA-N nonane-1-thiol Chemical compound CCCCCCCCCS ZVEZMVFBMOOHAT-UHFFFAOYSA-N 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 4
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 claims description 4
- CCIDWXHLGNEQSL-UHFFFAOYSA-N undecane-1-thiol Chemical group CCCCCCCCCCCS CCIDWXHLGNEQSL-UHFFFAOYSA-N 0.000 claims description 4
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims description 3
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical class CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 3
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical group CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004439 Isononyl alcohol Chemical group 0.000 claims description 3
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 claims description 3
- DILSSABZPPUWAZ-UHFFFAOYSA-N benzene;ethanethiol Chemical compound CCS.C1=CC=CC=C1 DILSSABZPPUWAZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- YIBKCPJOFAUAKY-UHFFFAOYSA-N cyclopropylsulfanylbenzene Chemical compound C1CC1SC1=CC=CC=C1 YIBKCPJOFAUAKY-UHFFFAOYSA-N 0.000 claims description 3
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 3
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 claims description 3
- VHKHNUDQGCOFAL-UHFFFAOYSA-N ethyl 4-ethyl-3-oxohexanoate Chemical compound CCOC(=O)CC(=O)C(CC)CC VHKHNUDQGCOFAL-UHFFFAOYSA-N 0.000 claims description 3
- PNAZUQUHTIOEHF-UHFFFAOYSA-N (3-methylphenyl)methanethiol Chemical group CC1=CC=CC(CS)=C1 PNAZUQUHTIOEHF-UHFFFAOYSA-N 0.000 claims description 2
- AGFYZLVFPSGUIX-UHFFFAOYSA-N (4-methylphenyl)methanethiol Chemical group CC1=CC=C(CS)C=C1 AGFYZLVFPSGUIX-UHFFFAOYSA-N 0.000 claims description 2
- UIYKSYBJKIMANV-UHFFFAOYSA-N (4-tert-butylphenyl)methanethiol Chemical group CC(C)(C)C1=CC=C(CS)C=C1 UIYKSYBJKIMANV-UHFFFAOYSA-N 0.000 claims description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 2
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims description 2
- XJIRSLHMKBUGMR-UHFFFAOYSA-N 1-ethylsulfanylbutane Chemical compound CCCCSCC XJIRSLHMKBUGMR-UHFFFAOYSA-N 0.000 claims description 2
- WCXXISMIJBRDQK-UHFFFAOYSA-N 1-methylsulfanylbutane Chemical compound CCCCSC WCXXISMIJBRDQK-UHFFFAOYSA-N 0.000 claims description 2
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 claims description 2
- RDOYGXODZMRGKD-UHFFFAOYSA-N 1-undecylsulfanylundecane Chemical compound CCCCCCCCCCCSCCCCCCCCCCC RDOYGXODZMRGKD-UHFFFAOYSA-N 0.000 claims description 2
- YTQWQAVWWKLCDR-UHFFFAOYSA-N 2,3-diethylpiperidine Chemical class CCC1CCCNC1CC YTQWQAVWWKLCDR-UHFFFAOYSA-N 0.000 claims description 2
- DRLFSUDDXLQHJT-UHFFFAOYSA-N 2,3-dimethylpiperidine Chemical compound CC1CCCNC1C DRLFSUDDXLQHJT-UHFFFAOYSA-N 0.000 claims description 2
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 claims description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 claims description 2
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 claims description 2
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 2
- ZOYHTWUFFGGARK-UHFFFAOYSA-N 2,6-ditert-butylpiperidine Chemical class CC(C)(C)C1CCCC(C(C)(C)C)N1 ZOYHTWUFFGGARK-UHFFFAOYSA-N 0.000 claims description 2
- ZYXNLVMBIHVDRH-UHFFFAOYSA-N 2-Methylpropyl 3-oxobutanoate Chemical compound CC(C)COC(=O)CC(C)=O ZYXNLVMBIHVDRH-UHFFFAOYSA-N 0.000 claims description 2
- PCNXNSPEWIRGJO-UHFFFAOYSA-N 2-butylpiperidine Chemical compound CCCCC1CCCCN1 PCNXNSPEWIRGJO-UHFFFAOYSA-N 0.000 claims description 2
- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical compound CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 claims description 2
- CMWSRWTXVQLHNX-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylsulfanyl)propane Chemical compound CC(C)CSCC(C)C CMWSRWTXVQLHNX-UHFFFAOYSA-N 0.000 claims description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- QOMFXOOKFCCSND-UHFFFAOYSA-N 2-phenylethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCC1=CC=CC=C1 QOMFXOOKFCCSND-UHFFFAOYSA-N 0.000 claims description 2
- YLUDSYGJHAQGOD-UHFFFAOYSA-N 3-ethylpiperidine Chemical compound CCC1CCCNC1 YLUDSYGJHAQGOD-UHFFFAOYSA-N 0.000 claims description 2
- JWEWNTJADCWFRP-UHFFFAOYSA-N 3-methyl-1-(3-methylbutylsulfanyl)butane Chemical compound CC(C)CCSCCC(C)C JWEWNTJADCWFRP-UHFFFAOYSA-N 0.000 claims description 2
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 claims description 2
- WOFAGNLBCJWEOE-UHFFFAOYSA-N Benzyl acetoacetate Chemical compound CC(=O)CC(=O)OCC1=CC=CC=C1 WOFAGNLBCJWEOE-UHFFFAOYSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 claims description 2
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical compound CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 2
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 claims description 2
- MEXKFCWMWJZDMF-UHFFFAOYSA-N n,n-dibutylacetamide Chemical compound CCCCN(C(C)=O)CCCC MEXKFCWMWJZDMF-UHFFFAOYSA-N 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical group CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 2
- IGMQODZGDORXEN-UHFFFAOYSA-N pentadecane-1-thiol Chemical group CCCCCCCCCCCCCCCS IGMQODZGDORXEN-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- HMPSOEYFMTWOFC-UHFFFAOYSA-N propane-2,2-dithiol Chemical compound CC(C)(S)S HMPSOEYFMTWOFC-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 2
- 229960002317 succinimide Drugs 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 2
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical group CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 claims description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 claims 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims 2
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical group SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 claims 1
- XPOCLMJKMPFRAM-UHFFFAOYSA-N 3-phenylpropyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCCC1=CC=CC=C1 XPOCLMJKMPFRAM-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 239000004440 Isodecyl alcohol Substances 0.000 claims 1
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 claims 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 1
- JWMLCCRPDOIBAV-UHFFFAOYSA-N chloro(methylsulfanyl)methane Chemical compound CSCCl JWMLCCRPDOIBAV-UHFFFAOYSA-N 0.000 claims 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims 1
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims 1
- IDZAUPYMMSSVHP-UHFFFAOYSA-N pentyl 3-oxobutanoate Chemical compound CCCCCOC(=O)CC(C)=O IDZAUPYMMSSVHP-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 229910001868 water Inorganic materials 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 239000001273 butane Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 229910015900 BF3 Inorganic materials 0.000 description 7
- 238000007730 finishing process Methods 0.000 description 7
- 229940100630 metacresol Drugs 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000010552 living cationic polymerization reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- RKYMVQJWYYOIJB-UHFFFAOYSA-N 1-decylsulfanyldecane Chemical class CCCCCCCCCCSCCCCCCCCCC RKYMVQJWYYOIJB-UHFFFAOYSA-N 0.000 description 2
- LEMIDOZYVQXGLI-UHFFFAOYSA-N 1-heptylsulfanylheptane Chemical class CCCCCCCSCCCCCCC LEMIDOZYVQXGLI-UHFFFAOYSA-N 0.000 description 2
- LHNRHYOMDUJLLM-UHFFFAOYSA-N 1-hexylsulfanylhexane Chemical compound CCCCCCSCCCCCC LHNRHYOMDUJLLM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical group C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QQAHAGNPDBPSJP-UHFFFAOYSA-N 1,1,1,2,2,3,3,3-octachloropropane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl QQAHAGNPDBPSJP-UHFFFAOYSA-N 0.000 description 1
- YFIIENAGGCUHIQ-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl YFIIENAGGCUHIQ-UHFFFAOYSA-N 0.000 description 1
- FTCVHAQNWWBTIV-UHFFFAOYSA-N 1,1,1,2,2-pentachloropropane Chemical compound CC(Cl)(Cl)C(Cl)(Cl)Cl FTCVHAQNWWBTIV-UHFFFAOYSA-N 0.000 description 1
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- INEMUVRCEAELBK-UHFFFAOYSA-N 1,1,1,2-tetrafluoropropane Chemical compound CC(F)C(F)(F)F INEMUVRCEAELBK-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- KMKSVAGOBVUFRO-UHFFFAOYSA-N 1-nonylsulfanylnonane Chemical class CCCCCCCCCSCCCCCCCCC KMKSVAGOBVUFRO-UHFFFAOYSA-N 0.000 description 1
- JOZDADPMWLVEJK-UHFFFAOYSA-N 1-pentylsulfanylpentane Chemical class CCCCCSCCCCC JOZDADPMWLVEJK-UHFFFAOYSA-N 0.000 description 1
- YZXSQDNPKVBDOG-UHFFFAOYSA-N 2,2-difluoropropane Chemical compound CC(C)(F)F YZXSQDNPKVBDOG-UHFFFAOYSA-N 0.000 description 1
- ROSSIHMZZJOVOU-UHFFFAOYSA-N 2-(methylthio)propane Chemical compound CSC(C)C ROSSIHMZZJOVOU-UHFFFAOYSA-N 0.000 description 1
- GZJUDUMQICJSFJ-UHFFFAOYSA-N 2-ethylsulfanyl-2-methylpropane Chemical compound CCSC(C)(C)C GZJUDUMQICJSFJ-UHFFFAOYSA-N 0.000 description 1
- CJFVCTVYZFTORU-UHFFFAOYSA-N 2-methyl-2-methylsulfanylpropane Chemical compound CSC(C)(C)C CJFVCTVYZFTORU-UHFFFAOYSA-N 0.000 description 1
- LNMBCRKRCIMQLW-UHFFFAOYSA-N 2-tert-butylsulfanyl-2-methylpropane Chemical compound CC(C)(C)SC(C)(C)C LNMBCRKRCIMQLW-UHFFFAOYSA-N 0.000 description 1
- XTMUXJBJCMRWPG-UHFFFAOYSA-N 3-chloropyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=C1Cl XTMUXJBJCMRWPG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NMTGXHFIJPOUOC-UHFFFAOYSA-N CN1CCNCC1.N1=CC=CC=C1 Chemical compound CN1CCNCC1.N1=CC=CC=C1 NMTGXHFIJPOUOC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000004411 aluminium Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 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
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- RKAJXYBSLYNRQZ-UHFFFAOYSA-N pentyl 3-oxohexanoate Chemical compound CCCCCOC(=O)CC(=O)CCC RKAJXYBSLYNRQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000008027 tertiary esters Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明涉及一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法，适用于异丁烯、异丁烯惰性溶剂混合液或含有异丁烯的混合轻C4馏分进行阳离子聚合制备高反应活性聚异丁烯。通过在聚合体系中引入有机化合物添加剂，达到高效选择性地脱除活性链末端碳正离子相邻‑CH3上β‑H，产生聚异丁烯链末端α‑双键结构，从而直接制备出高收率的高反应活性聚异丁烯，链末端α‑双键含量可高达90%以上。
Description
技术领域
本发明涉及一种四氯化钛共引发体系及采用该共引发体系引发异丁烯聚合制备高反应活性聚异丁烯的方法，特别是用于异丁烯、异丁烯惰性溶剂混合液或含有异丁烯的混合轻C4馏分进行阳离子聚合制备端基α-双键含量可达90%以上的高反应活性聚异丁烯的方法。
背景技术
由异丁烯制备聚异丁烯是典型的阳离子聚合反应。阳离子聚合反应中活性链末端碳正离子不稳定，易发生β-H脱除、向单体或其他物质的转移以及分子内异构化等一系列副反应，因此所制备的聚异丁烯末端α-双键含量通常小于10%（摩尔），称为普通聚异丁烯。只有通过改变活性链末端碳正离子周围反离子的性质，导致链末端-CH3上β-H高效选择性脱除，导致聚异丁烯链末端α-双键的形成与稳定。与普通聚异丁烯不同，当聚异丁烯链末端α-双键含量≥60%时，称为反应活性聚异丁烯。聚异丁烯链末端α-双键含量越高，反应效率越高，因此提高聚异丁烯产物中α-双键含量一直以来是合成高反应活性聚异丁烯的研究目标，并且着重从研究引发体系的角度来改变活性链末端碳正离子周围反离子的性质和提高α-双键含量。目前工业优级高反应活性聚异丁烯产品的分子量分布指数在2.0左右，且难以在保证高α-双键含量的情况下进一步降低分子量分布。高反应活性聚异丁烯通常用作中间体与马来酸酐等物质直接发生热加和反应，制备润滑油和燃料的添加剂。
工业上用于制备HRPIB的有效体系是基于三氟化硼（BF3）的引发体系。在公开技术中，所用的BF3·配合物引发体系通常是由BF3与3~20个碳原子的仲醇和/或4~20个碳原子的叔醚（至少一个叔碳原子与醚中的氧原子相连）配合组成，直接制备末端α-双键含量≥70%的HRPIB，可参见US4605808，US5068490，和DE4033196等专利。CN1323841A和CN101781377B公开了由BF3和含氧有机化合物配体（含羰基、酯基、环醇或烷基取代酚化合物）组成的引发体系及用于直接制备高反应活性聚异丁烯的方法。EP671419和CN1120049公开了在BF3与醇、叔醚或羧酸组成的引发体系下采用含有异丁烯和5%以上丁烯-1的混合C4馏分合成反应活性聚异丁烯的方法，该方法在反应前必须将混合C4馏分原料进行氢化异构化预处理，使丁烯-1及丁烯-2的含量降低到比预处理前至少低20%的水平，但氢化异构化预处理步骤温度、压力要求高，导致生产工序多、流程长，反应条件要求高，生产成本高。此外，BF3腐蚀性强、毒性强，且价格昂贵。
除了BF3共引发体系外，其他路易斯酸共引发体系也被用于制备反应活性聚异丁烯。CN101033275A、CN101613427A和CN101613423A公开了采用AlCl3与含氮、磷或/和含氧的有机物引发异丁烯聚合，可直接制备末端α-双键含量大于80%的高反应活性聚异丁烯。CN101955558A公开了一种采用FeCl3与含氧或含硫的有机物配合组成的引发体系，来直接制备末端α-双键含量大于75%的高反应活性聚异丁烯。对于TiCl4共引发体系，通常被用于异丁烯活性阳离子聚合及制备叔氯端末基聚异丁烯，参见J Polym.Sci.,Part A:Polym.Chem.,1986,25:1847-1869；Polym.Bull.,1986,15:317-323；Polym.Bull.,1988,20:413-419；J Macromol.Sci-Chem.,1989,A26:1099-1114;Macromolecules,1990,23:3909-3915。US5169914公开一种引发体系及其用于活性阳离子聚合的方法，该引发体系由叔酯、叔醚、叔醇或叔氯化物等引发剂（A）、路易斯酸（M为钛、铝、硼或锡，X为卤素，n为小于7的整数）及给电子数或DN值在25~50之间的给电子体（如：二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、六甲基磷三酰胺、N-甲基-2-吡咯烷酮或四甲基脲等）组成，通过引入具有特殊化学结构的引发剂和强给电子性的给电子体共同来抑制体系中杂质水可能引起的不可控引发，从而达到活性阳离子聚合和得到叔氯端基聚异丁烯产品。若要获得链末端为α-双键含量的高反应活性聚异丁烯，还需要将叔氯端基聚异丁烯进一步脱除氯化氢来制备，参见US0318624，但在脱除氯化氢的过程中不可避免地产生含有内双键的副产物。CN1277212A公开了可控阳离子聚合方法，在体系中存在微量水的条件下不需要外加引发剂就能实现烯烃聚合，其中路易斯酸与体系中水的摩尔比为2~50，可以合成预期分子量及窄分子量分布的聚异丁烯。CN101062962A公开了采用醇类或醚类有机化合物作为配合剂与TiCl4组成配合物催化剂引发异丁烯聚合，其中选用的醇类配合剂选自C1~C3醇，如：甲醇、乙醇、丙醇；醚类配合剂仅选自C3~C4醚，如：甲乙醚、乙醚，可直接制备出HRPIB，但对于非极性聚合体系，通常引发活性低，聚合物分子量偏高。
发明内容
本发明的一个目的是提供一种廉价易得的基于TiCl4的共引发体系。该TiCl4共引发体系包含H2O或/和HX（X=Cl或Br）、TiCl4及有机化合物添加剂。TiCl4与H2O的摩尔比为51~3000，优选为100~2600，更优选为400~2300；HX与TiCl4的摩尔比为0~0.4，优选为0~0.3，更优选为0~0.2；有机化合物添加剂与TiCl4的摩尔比为0.008~1.0，优选为0.01~0.8，更优选为0.03~0.7。所述有机化合物添加剂是由A或A和B两种组分组成，其中A为硫醇类、硫醚类、哌啶类、酰胺类、乙酰乙酸酯类或吡啶类化合物，B为酚类或醇类化合物。其中B为可选组分，组分B与组分A的摩尔比值为0~10，优选0~8，更优选为0~7。
所述的硫醇类化合物选自C2~C18的硫醇中的一种或几种的混合物，优选自乙硫醇、乙二硫醇、丙硫醇、丙二硫醇、2-丙基硫醇、正丁硫醇、仲丁硫醇、异丁硫醇、叔丁硫醇、丁二硫醇、戊硫醇、戊二硫醇、己硫醇、己二硫醇、庚硫醇、庚二硫醇、辛硫醇、辛二硫醇、壬硫醇、壬二硫醇、癸硫醇、癸二硫醇、苯甲硫醇、苯乙硫醇、三苯硫醇、苄基硫醇、邻苯二硫醇、3-甲基苄基硫醇、4-甲基苄基硫醇、4-叔丁基苄基硫醇、十一烷基硫醇、十二烷基硫醇、十四烷基硫醇、十五烷基硫醇或十八烷基硫醇，更优选辛硫醇、壬硫醇、癸硫醇、十一烷基硫醇、十二烷基硫醇、苯甲硫醇或苯乙硫醇。
所述的硫醚类化合物选自C2~C24的硫醚中的一种或几种的混合物，优选自甲硫醚、乙硫醚、正丙硫醚、异丙硫醚、二正丁基硫醚、二异丁基硫醚、二叔丁基硫醚、二正戊基硫醚、二异戊基硫醚、二正己基硫醚、二异己基硫醚、二正庚基硫醚、二异庚基硫醚、二正辛基硫醚、二异辛基硫醚、二正壬基硫醚、二异壬基硫醚、二正癸基硫醚、二异癸基硫醚、正十一烷基硫醚、正十二烷基硫醚、甲基乙基硫醚、甲基正丙基硫醚、甲基异丙基硫醚、甲基正丁基硫醚、甲基叔丁基硫醚、乙基正丙基硫醚、乙基异丙基硫醚、乙基正丁基硫醚、乙基叔丁基硫醚、二甲基三硫醚、氯甲基甲基硫醚、甲基三硫醚、苯甲硫醚、苯乙硫醚、环丙基苯硫醚、二苯硫醚、2-甲基二苯硫醚、4-甲基二苯硫醚、4-叔丁基二苯硫醚或二苄基硫醚，更优选二叔丁基硫醚、十一烷基硫醚、十二烷基硫醚、苯甲硫醚、苯乙硫醚、环丙基苯硫醚、二苯硫醚、2-甲基二苯硫醚或4-甲基二苯硫醚。
所述的哌啶类化合物选自C5~C15的哌啶中的一种或几种的混合物，优选自哌啶、2-甲基哌啶、3-甲基哌啶、4-甲基哌啶、2,3-二甲基哌啶、2,4-二甲基哌啶、2,6-二甲基哌啶、2-乙基哌啶、2-丙基哌啶、2-丁基哌啶、3-乙基哌啶、4-乙基哌啶、2,3-二乙基哌啶、2,4-二乙基哌啶、2,6-二乙基哌啶或2,6-二叔丁基哌啶，更优选2-甲基哌啶、4-甲基哌啶、2,4-二甲基哌啶、2-乙基哌啶、4-乙基哌啶或2,4-二乙基哌啶。
所述的酰胺类化合物选自C3~C10的酰胺中的一种或几种的混合物，优选自N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、N,N-二正丙基甲酰胺、N,N-二丁基乙酰胺或N,N-二甲基丙酰胺，更优选N,N-二甲基甲酰胺、N,N-二甲基乙酰胺。
所述的乙酰乙酸酯类化合物选自C4~C10的乙酰乙酸酯中的一种或几种的混合物，优选自乙酰乙酸甲酯、乙酰乙酸乙酯、乙基乙酰乙酸乙酯、二乙基乙酰乙酸乙酯、乙酰乙酸丙酯、乙酰乙酸丁酯、乙酰乙酸异丁酯、乙酰乙酸戊酯、乙酰乙酸己酯、乙酰乙酸苄酯、乙酰乙酸苯乙基酯或乙酰乙酸苯丙基酯，更优选乙酰乙酸甲酯、乙酰乙酸乙酯、乙基乙酰乙酸乙酯、二乙基乙酰乙酸乙酯、乙酰乙酸丙酯或乙酰乙酸丁酯。
所述的吡啶类化合物选自C5~C15的哌啶中的一种或几种的混合物，优选自吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2,3-二甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、2-乙基吡啶、2-丙基吡啶、2-丁基吡啶、3-乙基吡啶、4-乙基吡啶、2,3-二乙基吡啶、2,4-二乙基吡啶、2,6-二乙基哌啶或2,6-二叔丁基吡啶，更优选2-甲基吡啶、4-甲基吡啶、2,4-二甲基吡啶、2-乙基吡啶、4-乙基吡啶或2,4-二乙基吡啶。
所述的醇类化合物选自C1~C10醇中的一种或几种的混合物，优选为：甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、丁二醇、正戊醇、异戊醇、环戊醇、季戊四醇、正己醇、异己醇、环己醇、己二醇、正庚醇、异庚醇、叔庚醇、正辛醇、异辛醇、环辛醇、叔辛醇、正壬醇、异壬醇、环壬醇、正葵醇、异葵醇、葵二醇、苯甲醇或苯乙醇，更优选异丁醇、异戊醇、异己醇、异庚醇、异辛醇、异壬醇或异葵醇。
所述的酚类化合物选自C6~C18的酚中的一种或几种的混合物，优选自苯酚、邻-甲酚、间-甲酚、对-甲酚、间-乙酚、对-乙酚、邻-氯代酚、间-氯代酚、对-氯代酚、2-乙基苯酚、3-乙基苯酚、4-乙基苯酚、2-丁基苯酚、邻-苯二酚、间-苯二酚、对-苯二酚、2,3-二甲基苯酚、2,4-二甲基苯酚、2,6-二甲基苯酚、2,6-二叔丁基-4-甲基苯酚或2,6-二叔丁基-4-乙基苯酚；更优选自邻-甲酚、间-甲酚、2,6-二甲基苯酚或2,6-二叔丁基-4-甲基苯酚。
本发明的另一个目的是提供一种所述TiCl4共引发体系用于制备高反应活性聚异丁烯的方法，在含异丁烯原料的阳离子聚合反应体系中，通过引入适量的有机化合物添加剂，如硫醇类、硫醚类、哌啶类、酰胺类、乙酰乙酸酯类或吡啶类化合物，降低反离子的酸性，增加亲核性及空间位阻，达到选择性地脱除活性链末端碳正离子相邻-CH3上β-H，从而产生聚异丁烯链末端α-双键结构，达到直接制备出末端α-双键含量可高达90%以上的高反应活性聚异丁烯。
上述的异丁烯原料可以是液相纯异丁烯、异丁烯惰性溶剂混合液或含异丁烯的混合C4馏分。C4馏分是石油裂解或催化裂化时产生的含异丁烯、1-丁烯、2-丁烯和丁烷等等4个C组分组成的烃类混合物，通常异丁烯浓度为1.5mol/L~5.3mol/L。C4馏分可以不需要进行氢化异构化处理而直接使用。根据一个实施方案，在异丁烯惰性溶剂混合液或含异丁烯的混合C4馏分中，异丁烯浓度范围为1.0mol/L~5.8mol/L，优选1.2mol/L~5.5mol/L，更优选1.4mol/L~5.4mol/L。异丁烯的惰性溶剂混合液所使用的惰性溶剂可以是饱和烃，如丁烷、戊烷、正己烷、环己烷、甲基环己烷、正辛烷和异辛烷，或者卤代烃，如一氯甲烷、二氯甲烷、三氯甲烷、一氯乙烷、二氯乙烷、三氯乙烷、四氯乙烷、氯丙烷、二氯丙烷、三氯丙烷、四氯丙烷、五氯丙烷、六氯丙烷、七氯丙烷、八氯丙烷、氯丁烷、二氯丁烷、二氟甲烷、三氟甲烷、二氟乙烷、三氟乙烷、四氟乙烷、五氟乙烷、六氟乙烷、二氟丙烷、三氟丙烷、四氟丙烷、五氟丙烷、六氟丙烷、七氟丙烷或八氟丙烷中的一种或几种组成的混合溶剂。当然，本领域技术人员也可以根据实际需要选择合适的含异丁烯聚合反应体系。
在本发明中，所述的四氯化钛共引发体系用量（以四氯化钛摩尔用量计）与异丁烯摩尔量的比为0.04~0.4，优选0.06~0.35，更优选0.08~0.30。四氯化钛与H2O或/和HX（X=Cl或Br）的用量是根据聚合产物分子量和反应温度而定的，除了其他因素外，聚异丁烯的分子量取决于四氯化钛及配合剂相对于所用的单体的量。应尽量降低四氯化钛及配合剂的用量，以减少不必要的异构化反应和降低成本。有机化合物添加剂的用量与其亲核性强弱及其取代基结构的空间位阻有关，也决定了聚合产物的转化率、分子量、分子量分布及末端α-双键含量。有机化合物添加剂与TiCl4的摩尔比为0.008~1.0，优选为0.01~0.8，更优选为0.03~0.7。
所述的H2O、HX（X=Cl或Br）、有机化合物添加剂或TiCl4，可以直接使用，也可以用上述溶剂稀释后使用。本发明聚合反应可在常规反应器（如釜式反应器、管式反应器、环管式反应器、旋转床反应器等）中进行，先在含异丁烯的原料中加入H2O或/和HX（X=Cl或Br）以及所述的有机化合物添加剂，再加入TiCl4引发聚合。聚合温度为-50~25℃，优选-40~10℃，更优选-37~5℃。聚合反应时间为1~120min，优选2~100min，更优选3~70min，这取决于反应条件和聚合产物的性能指标。聚合反应一段时间后，反应液中加入过量的醇或/和碱性物质，如NaOH或氨的水溶液或者NaOH/乙醇溶液，终止聚合反应，分离未反应单体及溶剂等组分，用己烷/乙醇体系将产物反复溶解、沉淀，醇洗及水洗多次，将洗净的聚合产物真空干燥至恒重。称重聚合产物，并计算聚异丁烯产物收率。
用GPC测试聚合物（四氢呋喃溶剂体系）的数均分子量（Mn）、重均分子量（Mw）和分子量分布（PDI，Mw/Mn），用NMR表征和测定聚合物的端基结构（CDCl3溶剂，TMS标准剂）。
采用本发明的引发体系及制备方法，可以实现从异丁烯、异丁烯的烷烃类混合物或含有异丁烯的混合轻C4馏分进行阳离子聚合直接制备高反应活性聚异丁烯。高反应活性聚异丁烯的数均分子量在500~6000范围、分子量分布窄（分布指数可达1.2），链末端α-双键含量高于60mol%，较优高于80mol%，更优高于90mol%。
具体实施方式
提供以下非限制性实施例来进一步说明本发明，但本发明不限于这些实施例。
实施例1
在-28℃及高纯氮气保护下，在20mL含有异丁烯、正己烷、水和HCl的混合溶液中（[H2O]＝0.64mmol/L；[HCl]＝40.5mmol/L；[IB]＝3.0mol/L）依次加入3.84mmol2-苯乙硫醇和9.6mmol TiCl4，混合均匀，再加入，使得TiCl4与H2O的摩尔比为750，HCl与TiCl4的摩尔比为0.08，2-苯乙硫醇与TiCl4摩尔比为0.4，TiCl4与异丁烯的摩尔比为0.16，2-苯乙硫醇与异丁烯的摩尔比为0.066。聚合反应30min后，加入3mL0.1g/L的NaOH/乙醇溶液终止反应。聚合产物用乙醇沉淀，并用去离子水、乙醇反复洗涤，最后置于40℃真空烘箱干燥24h，得到高反应活性聚异丁烯（HRPIB）产品。HRPIB的收率为70%，数均分子量（Mn）为3200，分子量分布指数（PDI）为1.6，末端α双键含量为83%。
实施例2
在-32℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯、水和HCl的混合C4馏分（[H2O]=0.35mmol/L；[HCl]=40.5mmol/L；[IB]=2.9mol/L）溶液中依次加入5.8mmol的2-苯乙硫醇和12mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为1765，HCl与TiCl4的摩尔比为0.07，2-苯乙硫醇与TiCl4摩尔比为0.48，TiCl4与异丁烯的摩尔比为0.21，2-苯乙硫醇与异丁烯的摩尔比为0.099。反应40min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为21%，Mn为1500，PDI为1.2，末端α双键含量为91%。
实施例3
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯、水和HCl的混合C4馏分（[H2O]=0.35mmol/L；[HCl]=46.5mmol/L；[IB]=1.6mol/L）溶液中依次加入1.44mmol的正十二烷基硫醇和8mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为1176，HCl与TiCl4的摩尔比为0.12，正十二烷基硫醇与TiCl4摩尔比为0.18，TiCl4与异丁烯的摩尔比为0.25，正十二烷基硫醇与异丁烯的摩尔比为0.046。反应50min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为18%，Mn为2000，PDI为1.2，末端α双键含量为89%。
实施例4
在0℃及高纯氮气保护下，在20mL含有异丁烯、正己烷、二氯甲烷、水和HCl的混合溶液中（[H2O]＝0.56mmol/L；[HCl]＝31mmol/L；[IB]＝2.0mol/L，正己烷/二氯甲烷=9/1，体积比）加入2.0mmol的正十二烷基硫醇，混合均匀，再加入10mmol TiCl4，使得TiCl4与H2O的摩尔比为893，HCl与TiCl4的摩尔比为0.06，正十二烷基硫醇与TiCl4摩尔比为0.2，TiCl4与异丁烯的摩尔比为0.25，正十二烷基硫醇与异丁烯的摩尔比为0.05。反应30min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为18%，数均分子量（Mn）为1200，分子量分布指数（PDI）为1.9，末端α双键含量为80%。
实施例5
在-27℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯、水和HCl的混合C4馏分（[H2O]=0.35mmol/L；[HCl]=27mmol/L；[IB]=2.9mol/L）溶液中依次加入1.44mmol的正十二烷基硫醇和12mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为1765，HCl与TiCl4的摩尔比为0.04，正十二烷基硫醇与TiCl4摩尔比为0.12，TiCl4与异丁烯的摩尔比为0.21，正十二烷基硫醇与异丁烯的摩尔比为0.025。反应5min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为42%，Mn为2000，PDI为1.3，末端α双键含量为87%。
实施例6
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯、水和HCl的混合C4馏分（[H2O]=0.35mmol/L；[HCl]=47mmol/L；[IB]=2.9mol/L）溶液中依次加入2.9mmol的苯甲硫醚和9.6mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为1412，HCl与TiCl4的摩尔比为0.10，苯甲硫醚与TiCl4摩尔比为0.3，TiCl4与异丁烯的摩尔比为0.16，苯甲硫醚与异丁烯的摩尔比为0.05，H2O与异丁烯的摩尔比为1.2×10-4，HCl与异丁烯的摩尔比为1.6×10-2。反应60min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为22%，Mn为2400，PDI为1.4，末端α双键含量为75%。
实施例7
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯、水和HCl的混合C4馏分（[H2O]=0.85mmol/L；[HCl]=40.5mmol/L；[IB]=3.0mol/L）溶液中依次加入0.48mmol的4-甲基哌啶和16mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为930，HCl与TiCl4的摩尔比为0.11，4-甲基哌啶与TiCl4摩尔比为0.05，TiCl4与异丁烯的摩尔比为0.27，4-甲基哌啶与异丁烯的摩尔比为0.014，H2O与异丁烯的摩尔比为3.0×10-4，HCl与异丁烯的摩尔比为1.4×10-2。反应60min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为12%，Mn为5400，PDI为1.9，末端α双键含量为68%。
实施例8
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯和水的混合C4馏分（[H2O]＝0.65mmol/L；[IB]＝3.0mol/L）溶液中依次加入2.98mmol的间甲酚、0.98mmol的N,N-二甲基乙酰胺和16mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为750，N,N-二甲基乙酰胺与TiCl4摩尔比为0.09，TiCl4与异丁烯的摩尔比为0.16，间甲酚与N,N-二甲基乙酰胺的摩尔比为3.0，N,N-二甲基乙酰胺与异丁烯的摩尔比为0.016。反应2min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为33%，Mn为3000，PDI为1.7，末端α双键含量为64%。
实施例9
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯和水的混合C4馏分（[H2O]＝0.65mmol/L；[IB]＝3.0mol/L）溶液中依次加入2.98mmol的间甲酚、1.88mmol的乙酰乙酸甲酯和9.6mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为750，乙酰乙酸甲酯与TiCl4摩尔比为0.16，TiCl4与异丁烯的摩尔比为0.16，间甲酚与乙酰乙酸甲酯的摩尔比为1.6，乙酰乙酸甲酯与异丁烯的摩尔比为0.03。反应20min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为20%，Mn为2300，PDI为1.6，末端α双键含量为69%。
实施例10
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯和水的混合C4馏分（[H2O]＝0.65mmol/L；[IB]＝2.9mol/L）溶液中依次加入4.32mmol的异戊醇、0.73mmol的N,N-二甲基乙酰胺和9.6mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为750，N,N-二甲基乙酰胺与TiCl4摩尔比为0.08，TiCl4与异丁烯的摩尔比为0.16，异戊醇与N,N-二甲基乙酰胺的摩尔比为5.8，N,N-二甲基乙酰胺与异丁烯的摩尔比为0.012。反应40min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为31%，Mn为2800，PDI为1.8，末端α双键含量为63%。
对比例
在-30℃及高纯氮气保护下，在20mL含有异丁烯、丁烷、丁烯、水和HCl的混合C4馏分（[H2O]＝1.1mmol/L；[IB]＝2.9mol/L）溶液中依次加入2.88mmol的间甲酚和9.6mmol TiCl4，混合均匀，使得TiCl4与H2O的摩尔比为436，间甲酚与TiCl4摩尔比为0.3，TiCl4与异丁烯的摩尔比为0.16，间甲酚与异丁烯的摩尔比为0.05。反应60min后终止聚合，终止方法及聚合物后处理方法同实施例1。HRPIB的收率为79%，Mn为1400，PDI为1.8，末端α双键含量为9%。
Claims (10)
1.一种四氯化钛共引发体系，包含TiCl4与H2O或/和HX及有机化合物添加剂，HX中的X＝Cl或Br，其中有机化合物添加剂由A或A和B两种组分组成，A为硫醇类、硫醚类、哌啶类、酰胺类、乙酰乙酸酯类或吡啶类化合物，B为酚类或醇类化合物，其中B为可选组分，组分B与组分A的摩尔比值为0～10；TiCl4与H2O的摩尔比为51～3000，HX与TiCl4的摩尔比为0～0.4，有机化合物添加剂与TiCl4的摩尔比为0.008～1.0。
2.根据权利要求1的四氯化钛共引发体系，其特征是：B与组分A的摩尔比值为0～8；TiCl4与H2O的摩尔比为100～2600，HX与TiCl4的摩尔比为0～0.3，有机化合物添加剂与TiCl4的摩尔比为0.01～0.8。
3.根据权利要求1或2的四氯化钛共引发体系，其特征是：TiCl4与H2O的摩尔比为400～2300，HX与TiCl4的摩尔比为0～0.2，有机化合物添加剂与TiCl4的摩尔比为0.03～0.7。
4.根据权利要求1的四氯化钛共引发体系，其特征是：硫醇类化合物选自C2～C18的硫醇中的一种或几种的混合物；硫醚类化合物选自C2～C24的硫醚中的一种或几种的混合物；哌啶类化合物选自C5～C15的哌啶中的一种或几种的混合物；酰胺类化合物选自C3～C10的酰胺中的一种或几种的混合物；乙酰乙酸酯类选自C4～C10的乙酰乙酸酯中的一种或几种的混合物；吡啶类化合物选自C5～C15的哌啶中的一种或几种的混合物；醇选自C1～C10醇中的一种或几种的混合物；所述的酚选自C6～C18的酚中的一种或几种的混合物。
5.根据权利要求4的四氯化钛共引发体系，其特征是：所述的硫醇类化合物选自乙硫醇、乙二硫醇、丙硫醇、丙二硫醇、2-丙基硫醇、正丁硫醇、仲丁硫醇、异丁硫醇、叔丁硫醇、丁二硫醇、戊硫醇、戊二硫醇、己硫醇、 己二硫醇、庚硫醇、庚二硫醇、辛硫醇、辛二硫醇、壬硫醇、壬二硫醇、癸硫醇、癸二硫醇、苯甲硫醇、苯乙硫醇、三苯硫醇、苄基硫醇、邻苯二硫醇、3-甲基苄基硫醇、4-甲基苄基硫醇、4-叔丁基苄基硫醇、十一烷基硫醇、十二烷基硫醇、十四烷基硫醇、十五烷基硫醇或十八烷基硫醇；
所述的硫醚类化合物选自甲硫醚、乙硫醚、正丙硫醚、异丙硫醚、二正丁基硫醚、二异丁基硫醚、二叔丁基硫醚、二正戊基硫醚、二异戊基硫醚、二正己基硫醚、二异己基硫醚、二正庚基硫醚、二异庚基硫醚、二正辛基硫醚、二异辛基硫醚、二正壬基硫醚、二异壬基硫醚、二正癸基硫醚、二异癸基硫醚、十一烷基硫醚、十二烷基硫醚、甲基乙基硫醚、甲基正丙基硫醚、甲基异丙基硫醚、甲基正丁基硫醚、甲基叔丁基硫醚、乙基正丙基硫醚、乙基异丙基硫醚、乙基正丁基硫醚、乙基叔丁基硫醚、二甲基三硫醚、氯甲基甲基硫醚、甲基三硫醚、苯甲硫醚、苯乙硫醚、环丙基苯硫醚、二苯硫醚、2-甲基二苯硫醚、4-甲基二苯硫醚、4-叔丁基二苯硫醚或二苄基硫醚；
所述的哌啶类化合物选自哌啶、2-甲基哌啶、3-甲基哌啶、4-甲基哌啶、2,3-二甲基哌啶、2,4-二甲基哌啶、2,6-二甲基哌啶、2-乙基哌啶、2-丙基哌啶、2-丁基哌啶、3-乙基哌啶、4-乙基哌啶、2,3-二乙基哌啶、2,4-二乙基哌啶、2,6-二乙基哌啶或2,6-二叔丁基哌啶；
所述的酰胺类化合物选自N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、N,N二正丙基甲酰胺、N,N-二丁基乙酰胺或N,N-二甲基丙酰胺；
所述的乙酰乙酸酯类化合物选自乙酰乙酸甲酯、乙酰乙酸乙酯、乙基乙酰乙酸乙酯、二乙基乙酰乙酸乙酯、乙酰乙酸丙酯、乙酰乙酸丁酯、乙酰乙酸异丁酯、乙酰乙酸戊酯、乙酰乙酸己酯、乙酰乙酸苄酯、乙酰乙酸苯乙基酯或乙酰乙酸苯丙基酯；
所述的吡啶类化合物选自吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2,3-二甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、2-乙基吡啶、2-丙基吡啶、2-丁基吡啶、3-乙基吡啶、4-乙基吡啶、2,3-二乙基吡啶、2,4-二乙基吡啶、2,6-二乙基哌啶或2,6-二叔丁基吡啶；
所述的醇类化合物选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、丁二醇、正戊醇、异戊醇、环戊醇、季戊四醇、正己醇、异己醇、环己醇、己二醇、正庚醇、异庚醇、叔庚醇、正辛醇、异辛醇、环辛醇、叔辛醇、正壬醇、异壬醇、环壬醇、正癸醇、异-癸醇、癸二醇、苯甲醇或苯乙醇；
所述的酚类化合物选自苯酚、邻-甲酚、间-甲酚、对-甲酚、间-乙酚、对-乙酚、邻-氯代酚、间-氯代酚、对-氯代酚、2-乙基苯酚、3-乙基苯酚、4-乙基苯酚、2-丁基苯酚、邻-苯二酚、间-苯二酚、对-苯二酚、2,3-二甲基苯酚、2,4-二甲基苯酚、2,6-二甲基苯酚、2,6-二叔丁基-4-甲基苯酚或2,6-二叔丁基-4-乙基苯酚。
6.根据权利要求5的四氯化钛共引发体系，其特征是：硫醇类化合物选自辛硫醇、壬硫醇、癸硫醇、十一烷基硫醇、十二烷基硫醇、苯甲硫醇或苯乙硫醇；硫醚类化合物选自十一烷基硫醚、十二烷基硫醚、苯甲硫醚、苯乙硫醚、环丙基苯硫醚、二苯硫醚、2-甲基二苯硫醚或4-甲基二苯硫醚；酰胺类化合物选自N,N-二甲基甲酰胺或N,N-二甲基乙酰胺；哌啶类化合物选自2-甲基哌啶、4-甲基哌啶、2,4-二甲基哌啶、2-乙基哌啶、4-乙基哌啶或2,4-二乙基哌啶；乙酰乙酸酯类化合物选自乙酰乙酸甲酯、乙酰乙酸乙酯、乙基乙酰乙酸乙酯、二乙基乙酰乙酸乙酯、乙酰乙酸丙酯或乙酰乙酸丁酯；吡啶类化合物选自2-甲基吡啶、4-甲基吡啶、2,4-二甲基吡啶、2-乙基吡啶、4-乙基吡啶或2,4-二乙基吡啶；醇类化合物选自异丁醇、异戊醇、异己醇、异庚醇、异辛醇、异壬醇或异癸醇；酚类化合物选自邻-甲酚、间-甲酚、2,6- 二甲基苯酚或2,6-二叔丁基-4-甲基苯酚。
7.一种采用权利要求1四氯化钛共引发体系制备高反应活性聚异丁烯的方法，在H2O或/和HX及有机化合物添加剂存在下，由TiCl4共引发异丁烯、异丁烯惰性溶剂混合液或含有异丁烯的混合轻C4馏分在-50～25℃下进行阳离子聚合反应1～120min，制备高反应活性聚异丁烯。
8.根据权利要求7的制备方法，其特征是：四氯化钛共引发体系用量以四氯化钛摩尔用量计与异丁烯摩尔量的比为0.04～0.4。
9.根据权利要求8的制备方法，其特征是：四氯化钛共引发体系用量以四氯化钛摩尔用量计与异丁烯摩尔量的比为0.06～0.35。
10.根据权利要求7的制备方法，其特征是：聚合温度为-40～10℃，聚合反应时间为2～100min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042536.5A CN103965381B (zh) | 2013-02-01 | 2013-02-01 | 一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042536.5A CN103965381B (zh) | 2013-02-01 | 2013-02-01 | 一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965381A CN103965381A (zh) | 2014-08-06 |
| CN103965381B true CN103965381B (zh) | 2016-08-24 |
Family
ID=51235422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310042536.5A Active CN103965381B (zh) | 2013-02-01 | 2013-02-01 | 一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965381B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0145235A1 (en) * | 1983-11-01 | 1985-06-19 | BP Chemicals Limited | Cationic polymerisation of 1-olefins |
| CN101613423A (zh) * | 2008-06-27 | 2009-12-30 | 北京化工大学 | 一种用于合成高反应活性聚异丁烯的引发体系 |
| CN102775534A (zh) * | 2011-05-13 | 2012-11-14 | 北京化工大学 | 一种制备高反应活性聚异丁烯的引发体系及应用 |
-
2013
- 2013-02-01 CN CN201310042536.5A patent/CN103965381B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0145235A1 (en) * | 1983-11-01 | 1985-06-19 | BP Chemicals Limited | Cationic polymerisation of 1-olefins |
| CN101613423A (zh) * | 2008-06-27 | 2009-12-30 | 北京化工大学 | 一种用于合成高反应活性聚异丁烯的引发体系 |
| CN102775534A (zh) * | 2011-05-13 | 2012-11-14 | 北京化工大学 | 一种制备高反应活性聚异丁烯的引发体系及应用 |
Non-Patent Citations (1)
| Title |
|---|
| "TiCl4共引发异丁烯正离子聚合合成反应活性聚异丁烯";林涛等;《高分子学报》;20080229(第2期);129-135 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965381A (zh) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5543447B2 (ja) | イソブチレン系重合体およびその製造方法 | |
| Patel et al. | Synthesis of alkyne‐terminated xanthate RAFT agents and their uses for the controlled radical polymerization of N‐vinylpyrrolidone and the synthesis of its block copolymer using click chemistry | |
| Kadokawa et al. | Ring‐Opening Polymerization of Ethylene Carbonate Catalyzed with Ionic Liquids: Imidazolium Chloroaluminate and Chlorostannate Melts | |
| EP3143056B1 (en) | Polyalkenyl coupling agent and conjugated diene polymers prepared therefrom | |
| CN104558304A (zh) | 生产高反应性烯烃官能聚合物的聚合引发体系和方法 | |
| Chen et al. | New Strategy Targeting Well‐Defined Polymethylene‐block‐Polystyrene Copolymers: The Combination of Living Polymerization of Ylides and Atom Transfer Radical Polymerization | |
| US20200031978A1 (en) | Polyolefin-Polystyrene Multi-Block Copolymer, Organozinc Compound for Preparing Same, and Method for Preparing Polyolefin-Polystyrene Multi-Block Copolymer | |
| Patel et al. | (S)‐2‐(ethyl propionate)‐(O‐ethyl xanthate)‐and (S)‐2‐(Ethyl isobutyrate)‐(O‐ethyl xanthate)‐mediated RAFT polymerization of vinyl acetate | |
| Yang et al. | Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co‐initiated with TiCl4 in nonpolar hydrocarbon media | |
| CN106232642B (zh) | 无规丙烯-乙烯共聚物 | |
| CN106905453A (zh) | 一种用于合成中高分子量聚异丁烯的复合催化剂、制备方法及聚合工艺 | |
| CN103965381B (zh) | 一种四氯化钛共引发体系及其用于制备高反应活性聚异丁烯的方法 | |
| CN106573996A (zh) | 作为用于丁基橡胶生产的稀释剂的氢氟烯烃(hfo) | |
| CN106574013A (zh) | 具有低类异戊二烯含量的共聚物 | |
| Huang et al. | Synthesis of twin‐tail tadpole‐shaped (cyclic polystyrene)‐block‐[linear poly (tert‐butyl acrylate)] 2 by combination of glaser coupling reaction with living anionic polymerization and atom transfer radical polymerization | |
| CN100523018C (zh) | 一种异烯烃聚合物或共聚物的制备方法 | |
| CN102372822B (zh) | 制备异单烯烃-多烯烃共聚物的方法 | |
| WO2012072643A3 (de) | Herstellung von isobutenhomo- oder -copolymer-derivaten | |
| CN101987877B (zh) | 一种立构聚合物的阳离子聚合方法 | |
| CN112646098B (zh) | 嵌段共聚物及其制备方法 | |
| CN110183560B (zh) | 一种利用铁钛复合催化剂制备中分子量聚异丁烯的方法 | |
| US7847020B2 (en) | Polyisobutene polyol and moulding compound | |
| Manju et al. | Synthesis and Characterization of Copolymers of Methyl Methacrylate and 2-Ethoxyethyl Methacrylate | |
| Dimitrov et al. | Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group | |
| CN107216414B (zh) | 一种用于合成聚异丁烯的复合催化剂及其制备方法与应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20140806 Assignee: Anqing Yicheng Chemical Technology Co.,Ltd. Assignor: BEIJING University OF CHEMICAL TECHNOLOGY Contract record no.: X2023980033519 Denomination of invention: A titanium tetrachloride co initiator system and its method for preparing highly reactive polyisobutylene Granted publication date: 20160824 License type: Exclusive License Record date: 20230314 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240221 Address after: 246002 West of Guangyulan Road, Economic Development Zone, Daguan District, Anqing City, Anhui Province Patentee after: Anqing Yicheng Chemical Technology Co.,Ltd. Country or region after: China Address before: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Patentee before: BEIJING University OF CHEMICAL TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right |