CN112679642A - Cycloolefin copolymer and preparation method thereof - Google Patents
Cycloolefin copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN112679642A CN112679642A CN202011549213.1A CN202011549213A CN112679642A CN 112679642 A CN112679642 A CN 112679642A CN 202011549213 A CN202011549213 A CN 202011549213A CN 112679642 A CN112679642 A CN 112679642A
- Authority
- CN
- China
- Prior art keywords
- norbornene
- dodecene
- alkyl
- cycloolefin
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 29
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 21
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims abstract description 20
- 230000009477 glass transition Effects 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- -1 cyclic olefin Chemical class 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 13
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 125000003282 alkyl amino group Chemical class 0.000 claims description 12
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 claims description 8
- PSCJIEZOAFAQRM-UHFFFAOYSA-N 5-chlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)CC1C=C2 PSCJIEZOAFAQRM-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- GNHVCDAPMWHFKG-UHFFFAOYSA-N 1-ethenyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C=C)C(OC)=C1 GNHVCDAPMWHFKG-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 5
- MKOSBHNWXFSHSW-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-en-5-ol Chemical compound C1C2C(O)CC1C=C2 MKOSBHNWXFSHSW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 4
- YNQXOOPPJWSXMW-UHFFFAOYSA-N 1-ethenyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C=C YNQXOOPPJWSXMW-UHFFFAOYSA-N 0.000 claims description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 4
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 claims description 4
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 4
- DWPPXNJBRSZQHD-UHFFFAOYSA-N 5-bromobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Br)CC1C=C2 DWPPXNJBRSZQHD-UHFFFAOYSA-N 0.000 claims description 4
- LVXDMUDXBUNBQY-UHFFFAOYSA-N 5-cyclohexylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1CCCCC1 LVXDMUDXBUNBQY-UHFFFAOYSA-N 0.000 claims description 4
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-UHFFFAOYSA-N 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentenylidene Natural products C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- TXFONIGDXLPYOB-UHFFFAOYSA-N 1,3,5-trichloro-2-ethenylbenzene Chemical compound ClC1=CC(Cl)=C(C=C)C(Cl)=C1 TXFONIGDXLPYOB-UHFFFAOYSA-N 0.000 claims description 3
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 claims description 3
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 claims description 3
- UFMLLTODLZCTMW-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentamethylbenzene Chemical compound CC1=C(C)C(C)=C(C=C)C(C)=C1C UFMLLTODLZCTMW-UHFFFAOYSA-N 0.000 claims description 3
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical compound CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-N 0.000 claims description 3
- ZJSKEGAHBAHFON-UHFFFAOYSA-N 1-ethenyl-3-fluorobenzene Chemical compound FC1=CC=CC(C=C)=C1 ZJSKEGAHBAHFON-UHFFFAOYSA-N 0.000 claims description 3
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 claims description 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 3
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 claims description 3
- CZYVCAJKUNEWLC-UHFFFAOYSA-N 2-(5-bicyclo[2.2.1]hept-2-enyl)ethanol Chemical compound C1C2C(CCO)CC1C=C2 CZYVCAJKUNEWLC-UHFFFAOYSA-N 0.000 claims description 3
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- WLCBPITVIPSVKN-UHFFFAOYSA-N 4-(5-bicyclo[2.2.1]hept-2-enyl)butan-1-ol Chemical compound C1C2C(CCCCO)CC1C=C2 WLCBPITVIPSVKN-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- FXVHAJRVIMCUTP-UHFFFAOYSA-N 4-chloro-1-ethenyl-2-methoxybenzene Chemical compound COC1=CC(Cl)=CC=C1C=C FXVHAJRVIMCUTP-UHFFFAOYSA-N 0.000 claims description 3
- BPVVTRJJQZINNG-UHFFFAOYSA-N 4-chloro-1-ethenyl-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1C=C BPVVTRJJQZINNG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 claims description 3
- BKKJBUGUSRGLHB-UHFFFAOYSA-N 5-butoxybicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(OCCCC)CC1C=C2 BKKJBUGUSRGLHB-UHFFFAOYSA-N 0.000 claims description 3
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 claims description 3
- GSOYZECNEHYJMT-UHFFFAOYSA-N 5-chloro-2-ethenyl-1,3-dimethylbenzene Chemical compound CC1=C(C=C)C(=CC(=C1)Cl)C GSOYZECNEHYJMT-UHFFFAOYSA-N 0.000 claims description 3
- LLNJETIYJIMHAV-UHFFFAOYSA-N 5-ethoxybicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(OCC)CC1C=C2 LLNJETIYJIMHAV-UHFFFAOYSA-N 0.000 claims description 3
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 claims description 3
- RCDOWRWNYHNLLA-UHFFFAOYSA-N 5-methoxybicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(OC)CC1C=C2 RCDOWRWNYHNLLA-UHFFFAOYSA-N 0.000 claims description 3
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 3
- LFBHYIUTPVORTR-UHFFFAOYSA-N 5-fluorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(F)CC1C=C2 LFBHYIUTPVORTR-UHFFFAOYSA-N 0.000 claims description 2
- ZHYKGDVWCSPZMW-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-en-3-ol Chemical compound C1CC2C(O)=CC1C2 ZHYKGDVWCSPZMW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 2
- FCCGTJAGEHZPBF-UHFFFAOYSA-N ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCC)CC1C=C2 FCCGTJAGEHZPBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 9
- 229920000642 polymer Polymers 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZBCGOBOCBIVQBC-UHFFFAOYSA-N 1H-imidazole quinolin-2-amine Chemical compound NC1=NC2=CC=CC=C2C=C1.N1C=NC=C1 ZBCGOBOCBIVQBC-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000006310 cycloalkyl amino group Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RNWDNEVYZAPIBG-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-4-carboxylate Chemical compound C1CC2C=CC1(C(=O)OC)C2 RNWDNEVYZAPIBG-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the field of cyclic olefin copolymers, and more particularly, to a cyclic olefin copolymer having a structural unit of (a)
And (b)
And/or
Description
Technical Field
The invention relates to the field of cyclic olefin copolymers, in particular to a cyclic olefin copolymer and a preparation method thereof.
Background
Cycloolefin copolymers are widely used in the fields of packaging, optics, medical treatment, information, and the like because of their high light transmittance, chemical resistance, low dielectric constant, low birefringence, and high barrier properties.
Cycloolefin copolymers can be prepared by copolymerizing a cycloolefin with an alpha-olefin (e.g., ethylene, propylene, etc.). However, the addition of an α -olefin as a comonomer lowers the glass transition temperature of the copolymer and lowers the heat resistance. The cycloolefin copolymer obtained by copolymerizing the styrene monomer and the cycloolefin has higher glass transition temperature and can maintain the optical performance. Therefore, there is interest in the academic and industrial community for copolymers of cycloolefins with styrenic monomers. The copolymerization of cycloolefin and styrene monomer can adopt the catalytic system for the copolymerization of cycloolefin and alpha-olefin, but the catalytic systems not only have low polymerization activity but also have weak copolymerization capacity to styrene, and the obtained copolymer has low styrene content and poor controllability of copolymer performance (J.Polym.Sci.part A: Polym.Chem.,2011,49, 65).
When the late transition metal catalyst is used for catalyzing the copolymerization of the styrene monomer and the cycloolefin, the late transition metal catalyst has good copolymerization capacity on the styrene monomer, can obtain a copolymer with high styrene monomer content, but has lower molecular weight and can not meet the industrial application requirements (J.Polym.Sci.part A:2006,44, 5237). In the Chinese patent CN201610693531, a transition metal complex with quinolinamine imidazole ligand is used as a catalyst, a cycloolefin/styrene monomer copolymer with a relatively large molecular weight can be prepared, the number average molecular weight (Mn) is in the range of 7000-.
Disclosure of Invention
In view of the problems of the prior art, the first aspect of the present invention provides a cycloolefin copolymer having the structural unit of
Wherein R is1-R3Each independently selected from hydrogen, halogen, hydroxyl, amino, nitro and C1-10Alkyl of (A), C1-6Alkoxy group of (C)1-12Any one of mono-substituted or di-substituted alkylamino, R4Is selected from any one of hydrogen, halogen, hydroxyl, C1-6 alkyl, C1-6 alkoxy and C1-6 ester group, n is an integer of 1-4, and m is 0 or 1; the glass transition temperature of the cycloolefin copolymer is 100-400 ℃, and the number average molecular weight is 1000-10000000; the molecular weight distribution is 1.1-3.5.
As a preferable technical scheme of the invention, the preparation raw materials of the cycloolefin copolymer comprise 0.1-99.9 parts by weight of styrene monomers shown in a formula (1), 0.1-99.9 parts by weight of cycloolefin monomers shown in a formula (2) and/or a formula (3), a catalyst shown in a formula (4) and a cocatalyst;
As a preferred technical scheme of the invention, the cocatalyst is alkyl aluminum and/or alkyl aluminoxane.
In a preferred embodiment of the present invention, the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, tri-n-propyl aluminum, tri-n-butyl aluminum, and triisobutyl aluminum.
As a preferred technical scheme of the invention, the alkylaluminoxane is selected from one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
As a preferable technical means of the present invention, R is5、R6Each independently selected from any one of hydrogen, chlorine, bromine, methyl, ethyl, n-butyl, trifluoromethyl and tert-butyl; r7-12Each independently selected from hydrogen, chlorine, bromine, methyl, ethyl, n-butyl, tert-butyl, isopropyl, trifluoromethyl, phenyl, p-methylphenyl, p-ethylphenyl, p-butylphenyl, methoxy, ethoxy, butoxy, phenoxy, dimethylamino, diethylamino, dibutylamineAny one of a mesityl group, dihexylamino group, didecylamino group, p-methylphenoxy group, and p-butylphenoxy group; m is chromium or nickel; x1、X2Each independently selected from any one of chlorine, methyl, butyl, phenyl, benzyl and phenethyl.
In a preferred embodiment of the present invention, the styrenic monomer is selected from the group consisting of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 3-dimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,4,5, 6-pentamethylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2, 4-dimethoxystyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4, 6-trichlorostyrene, 2-methyl 4-chlorostyrene, 2, 4-chlorostyrene, 2-methyl styrene, and 2, 6-trimethylstyrene, 2, 6-dimethyl-4-chlorostyrene, 2-methoxy-4-chlorostyrene, 2, 6-dimethoxy-4-chlorostyrene.
As a preferred embodiment of the present invention, the cycloolefin monomer is selected from the group consisting of cyclopentene, cyclohexene, norbornene, 5-hydroxy-2-norbornene, 5-chloro-2-norbornene, 5-bromo-2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-methoxy-2-norbornene, 5-ethoxy-2-norbornene, 5-butoxy-2-norbornene, 5-hydroxymethyl-2-norbornene, 5-hydroxy-2-norbornene, 5-chloro-2-norbornene, 5-fluoro-2-norbornene, 5, 5-hydroxyethyl-2-norbornene, 5-hydroxybutyl-2-norbornene, 5-carbomethoxy-2-norbornene, 5-carbethoxy-2-norbornene, 5-carbomethoxy-2-norbornene, tetracyclododecene, 9-hydroxytetracyclo-4-dodecene, 9-chlorotetracyclo-4-dodecene, 9-bromo-4-dodecene, 9-methyltetracyclo-4-dodecene, 9-ethyltetracyclo-4-dodecene, 9-butyltetracyclo-4-dodecene, 9-hexyltetracyclo-4-dodecene, 9-cyclohexyltetracyclo-4-dodecene, 9-methoxytetracyclo-4-dodecene, 2-hydroxynorbornene, 5-carbomethoxy-2-norbornene, 5-carbomethoxy-2, 9-ethoxy tetracyclo-4-dodecene, 9-butoxy tetracyclo-4-dodecene, 9-hydroxymethyl tetracyclo-4-dodecene, 9-hydroxyethyl tetracyclo-4-dodecene, 9-hydroxybutyl tetracyclo-4-dodecene, 9-carbomethoxytetracyclo-4-dodecene, 9-carbethoxytetracyclo-4-dodecene and 9-butyltetracyclo-4-dodecene.
In a preferred embodiment of the present invention, the raw material for preparing the cyclic olefin further comprises a chain transfer agent, wherein the chain transfer agent is one or more selected from hydrogen, diethyl zinc and aluminum alkyl.
The second aspect of the present invention provides a method for preparing the cycloolefin copolymer, which comprises: mixing the preparation raw materials of the cycloolefin copolymer, and reacting at 20-100 deg.C under 0.1-100 atm.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts styrene monomer and cycloolefin monomer to copolymerize, prepare cycloolefin copolymer, the polymerization system is high in activity, the structure and characteristic of the polymer, such as molecular weight, molecular weight distribution, cycloolefin content, glass transition temperature, etc. can be adjustable in a large range, meanwhile, the number average molecular weight of cycloolefin in the invention can reach the industrial application requirement, in addition, the said method for preparing cycloolefin copolymer of the invention is suitable for the industrial production condition and processing shaping method of the polymer at present.
Detailed Description
The invention provides a cycloolefin copolymer in a first aspect, the structural unit of the cycloolefin copolymer is
Wherein R is1-R3Are respectively and independently selected from any one of hydrogen, halogen, hydroxyl, amino, nitro, C1-10 alkyl, C1-6 alkoxy and C1-12 mono-substituted or di-substituted alkylamino, R4Is selected from any one of hydrogen, halogen, hydroxyl, C1-6 alkyl, C1-6 alkoxy and C1-6 ester group, n is an integer of 1-4, and m is 0 or 1; the glass transition temperature of the cycloolefin copolymer is 100-400 ℃, and the number average molecular weight is 1000-10000000; the molecular weight distribution is 1.1-3.5.
In one embodiment, the content of the structural unit (b) in the cycloolefin copolymer is from 10 to 90% by weight.
The number average molecular weight range of the polymer can be controlled in a large range, the application range of the polymer is favorably widened, and the required molecular weight can be determined according to the requirements under different conditions. The molecular weight distribution can be adjusted in a wide range, and the preparation method is very beneficial to preparing polymers with different functions. When the molecular weight distribution is small (such as 1.1), the polymerization reaction is prone to active polymerization, the molecular weight difference among different molecular chains is small, the polymer is more uniform, and the block copolymers with different block structures can be prepared by segmented feeding. When the molecular weight distribution is large (such as 2.5), the rheological property of the polymer is improved, and the processing and forming are facilitated. The content of the cycloolefin can be in a wide range, and polymers with different glass transition temperatures can be prepared so as to meet the use requirements at different temperatures.
In one embodiment, the raw materials for preparing the cyclic olefin copolymer comprise 0.1-99.9 parts by weight of styrene monomers shown in formula (1), 0.1-99.9 parts by weight of cyclic olefin monomers shown in formula (2) and/or formula (3), a catalyst shown in formula (4) and a cocatalyst.
The contents of the catalyst and the cocatalyst in the preparation of the raw material are described below.
In one embodiment, the catalyst has a concentration of 10-6-10-4mol/L。
Preferably, the molar ratio of the total amount of the cycloolefin monomer and the styrene-based monomer to the catalyst is (10)2-105)：1。
In one embodiment, the promoter is present at a concentration of 10-4-10-2mol/L。
Preferably, the molar ratio of the cocatalyst to the catalyst is (10)2-104):1。
preferably, the halogen is selected from any one of fluorine, chlorine and bromine.
Preferably, the C1-10 alkyl group is selected from any one of linear alkyl hydroxyl, branched hydroxyalkyl, naphthenic hydroxyl and aromatic hydroxyl.
Preferably, the alkoxy of C1-6 is selected from any one of the linear alkoxy of C1-6, the branched alkoxy of C1-6 and the cycloalkoxy of C1-6.
Preferably, the C1-12 mono-or di-substituted alkylamino group is selected from C1-12 mono-or di-substituted straight-chain alkylamino group, C1-12 mono-or di-substituted branched-chain alkylamino group, and C1-12 mono-or di-substituted cycloalkylamino group.
In one embodiment, the styrenic monomer is selected from the group consisting of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 3-dimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,4,5, 6-pentamethylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2, 4-dimethoxystyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4, 6-trichlorostyrene, 2-methyl 4-chlorostyrene, 2, 6-dimethyl-4-chlorostyrene, 2-methoxy-4-chlorostyrene, 2, 6-dimethoxy-4-chlorostyrene.
Preferably, the styrene monomer is selected from one or more of styrene, p-methoxystyrene and p-chlorostyrene; more preferably, the styrenic monomer is styrene.
The styrene has high polymerization activity in the catalyst system of the invention, and the molar insertion rate of the final styrene in the cycloolefin copolymer is high, so that the cycloolefin copolymer has larger adjustable range characteristics such as number average molecular weight, molecular weight distribution, glass transition temperature and the like.
In one embodiment, the formula (2) is cyclopentene or cyclohexene.
In one embodiment, the formula (3) is selected from the group consisting of norbornene, 5-hydroxy-2-norbornene, 5-chloro-2-norbornene, 5-bromo-2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-methoxy-2-norbornene, 5-ethoxy-2-norbornene, 5-butoxy-2-norbornene, 5-hydroxymethyl-2-norbornene, 5-hydroxyethyl-2-norbornene, 5-chloro-2-norbornene, 5-bromo-2-norbornene, 5-chloro-2-norbornene, 5-hexyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-hydroxybutyl-2-norbornene, 5-carbomethoxy-2-norbornene, tetracyclododecene, 9-hydroxytetracyclo-4-dodecene, 9-chlorotetracyclo-4-dodecene, 9-bromo-4-dodecene, 9-methyltetracyclo-4-dodecene, 9-ethyltetracyclo-4-dodecene, 9-butyltetracyclo-4-dodecene, 9-hexyltetracyclo-4-dodecene, 9-cyclohexyltetracyclo-4-dodecene, 9-methoxytetracyclo-4-dodecene, 9-ethoxytetracyclo-4-dodecene, 2-norbornene, 5-carbomethoxy-2-norbornene, 5-carbomethoxy, 9-butoxy tetracyclo-4-dodecene, 9-hydroxymethyl tetracyclo-4-dodecene, 9-hydroxyethyl tetracyclo-4-dodecene, 9-hydroxybutyl tetracyclo-4-dodecene, 9-carbomethoxytetracyclo-4-dodecene, 9-carbethoxytetracyclo-4-dodecene and/or 9-butyltetracyclo-4-dodecene.
Preferably, the formula (3) is norbornene, methylnorbornene, carbomethoxynorbornene, tetracyclododecene, methyltetracyclododecene; more preferably, the formula (3) is norbornene.
The norbornene is easier to obtain, the degree of polymerization between the norbornene and styrene is controllable, and the parameter performance of the cycloolefin copolymer can be conveniently adjusted.
Preferably, said R is5、R6Each independently selected from any one of hydrogen, chlorine, bromine, methyl, ethyl, n-butyl, trifluoromethyl and tert-butyl; r7-12Each independently selected from any one of hydrogen, chlorine, bromine, methyl, ethyl, n-butyl, tert-butyl, isopropyl, trifluoromethyl, phenyl, p-methylphenyl, p-ethylphenyl, p-butylphenyl, methoxy, ethoxy, butoxy, phenoxy, dimethylamino, diethylamino, dibutylamino, dihexylamino, didecylamino, p-methylphenoxy and p-butylphenoxy; m is chromium or nickel; x1、X2Each independently selected from any one of chlorine, methyl, butyl, phenyl, benzyl and phenethyl.
The applicant has unexpectedly found that if a catalyst system for the copolymerization of a conventional cycloolefin and an α -olefin is used in the polymerization of a cycloolefin monomer and a styrene monomer, the resultant copolymer has low reactivity of styrene and poor adjustability of the molecular structure of the copolymer
When catalyzing cycloolefin monomer and styrene monomer, the catalytic activity is high, the types and contents of cycloolefin monomer and styrene monomer can be adjusted, the molecular weight, molecular weight distribution and glass transition temperature of cycloolefin copolymer can be fully adjusted, and meanwhile, cycloolefin copolymer with high molecular weight can be obtainedThe performance is high, and the steric hindrance of the catalyst is regulated, so that the structure of the polymer can be regulated under stable catalytic activity in the process of catalyzing the polymerization of the cycloolefin monomer and the styrene monomer, and the copolymer with high molecular weight can be obtained.
In one embodiment, the cocatalyst is an aluminum alkyl and/or an alkylaluminoxane.
Preferably, the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, diethyl aluminum monochloride, ethyl aluminum dichloride, tri-n-propyl aluminum, tri-n-butyl aluminum and triisobutyl aluminum.
Preferably, the alkylaluminoxane is selected from one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
In one embodiment, the cocatalyst is methylaluminoxane.
The combined action of the methylaluminoxane and the catalyst increases the catalytic activity on the cycloolefin monomer and the styrene monomer, improves the copolymerization capacity of the styrene, and obtains the cycloolefin copolymer with higher number average molecular weight.
In one embodiment, the raw material for preparing the cyclic olefin further comprises a chain transfer agent selected from one or more of hydrogen, diethyl zinc, and aluminum alkyl.
Preferably, the aluminoxane is selected from one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
In the preparation of the cycloolefin copolymer, a chain transfer agent may or may not be added.
In one embodiment, the styrenic monomer is a liquid and the cycloolefin monomer is a liquid.
In one embodiment, the raw material for preparing the cyclic olefin copolymer further includes a solvent.
Preferably, the solvent is selected from alkanes of C1-20, cycloalkanes of C1-20, aromatics of C1-20 and halogenated hydrocarbons of C1-20.
The alkane of C1-20 is n-hexane and/or n-heptane.
The C1-20 cycloalkane is cyclohexane and/or cycloheptane.
The aromatic hydrocarbon of C1-20 is selected from any one of toluene, xylene and ethylbenzene.
The C1-20 halogenated hydrocarbon is dichloroethane and/or chlorobenzene.
In one embodiment, the solvent is toluene.
The content of the solvent in the present invention is not particularly limited and may be selected conventionally by those skilled in the art.
In one embodiment, the method of preparing a cyclic olefin copolymer comprises: mixing the preparation raw materials of the cycloolefin copolymer, and reacting at 20-100 deg.C under 0.1-100 atm.
In the process for preparing the cycloolefin copolymer according to the present invention, the pressure is not particularly limited, and those skilled in the art can make a routine choice from the description in the present application.
In a preferred embodiment, the method for preparing the cyclic olefin copolymer comprises: adding solvent, cocatalyst, cycloolefin monomer, styrene monomer, and catalyst in nitrogen atmosphere, and reacting at 70 deg.C for 1-200 min.
In a more preferred embodiment, the method for preparing the cyclic olefin copolymer comprises: adding a solvent, a cocatalyst, a cycloolefin monomer and a styrene monomer in a nitrogen atmosphere, adding a catalyst, reacting at 70 ℃ for 30min to obtain a reaction solution, adding the reaction solution into acidified ethanol, stopping the reaction, and filtering, washing and drying the precipitated cycloolefin copolymer to obtain the cycloolefin copolymer.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Examples 1 to 3
Examples 1 to 3 of the present invention each provide a cycloolefin copolymer.
The preparation method of the cycloolefin copolymer comprises the following steps: in a 150mL glass bottle, a solvent (toluene), 1mL of a cocatalyst (10 wt% methylaluminoxane solution in toluene), a cycloolefin monomer (norbornene), and a styrene monomer (styrene) were added in a nitrogen atmosphere to make the total volume 50mL, and 1umol of a catalyst (R) was further added5-12Is hydrogen, M is chromium, X1、X2Chlorine) at 70 deg.C for 30 min; and adding the obtained reaction solution into acidified ethanol, stopping the reaction, filtering, washing and drying the precipitated cyclic olefin copolymer to obtain the cyclic olefin copolymer.
The monomer charge of the polymerization, the quality of the cycloolefin copolymer obtained, and the content of structural unit (a) in the polymer1HNMR determination), glass transition temperature (Tg, determined by DSC) data for the cycloolefin copolymers are given in table 1 below:
TABLE 1
Examples 4 to 8
Examples 4 to 8 of the present invention each provide a cycloolefin copolymer.
The preparation method of the cycloolefin copolymer comprises the following steps: a500 mL glass bottle was charged with solvent (toluene), 4mL of cocatalyst (10 wt% methylaluminoxane in toluene), 18.8g (0.20mol) of cycloolefin monomer (norbornene), and 20.84g (0.20mmol) of styrene monomer (styrene) under a nitrogen atmosphere to make the total volume 200mL, and 4umol of catalyst (R) was added5-12Is hydrogen, M is chromium, X1、X2Chlorine) and carrying out polymerization reaction for 30min under certain temperature conditions; and adding the obtained reaction solution into acidified ethanol, stopping the reaction, filtering, washing and drying the precipitated cyclic olefin copolymer to obtain the cyclic olefin copolymer.
The cyclic olefin copolymer obtained by the polymerization reaction has the content of the structural unit (a)1HNMR determination), polymer molecular weight distribution data are shown in table 2 below:
TABLE 2
Examples 9 to 12
Examples 9 to 12 of the present invention each provide a cycloolefin copolymer.
The preparation method of the cycloolefin copolymer comprises the following steps: a500 mL glass bottle was charged with solvent (toluene), 4mL of cocatalyst (10 wt% methylaluminoxane in toluene), 18.8g (0.20mol) of cycloolefin monomer (norbornene), and 20.84g (0.20mmol) of styrene monomer (styrene) under a nitrogen atmosphere to make the total volume 200mL, and 4umol of catalyst (X) of the corresponding structure was added1、X2Chlorine) at 70 deg.C for 30 min; and adding the obtained reaction solution into acidified ethanol, stopping the reaction, filtering, washing and drying the precipitated cyclic olefin copolymer to obtain the cyclic olefin copolymer.
The structure of the catalyst substituent used, the quality of the copolymer obtained, the content of structural unit (a) in the polymer1HNMR), polymer glass transition temperature (Tg) (as determined by DSC) data are shown in table 3 below:
TABLE 3
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A cycloolefin copolymer characterized in that the structural unit of the cycloolefin copolymer is (a)
And (b)
And/or
Wherein R is1-R3Are respectively and independently selected from any one of hydrogen, halogen, hydroxyl, amino, nitro, C1-10 alkyl, C1-6 alkoxy and C1-12 mono-substituted or di-substituted alkylamino, R4Is selected from any one of hydrogen, halogen, hydroxyl, C1-6 alkyl, C1-6 alkoxy and C1-6 ester group, n is an integer of 1-4, and m is 0 or 1; the glass transition temperature of the cycloolefin copolymer is 100-400 ℃, and the number average molecular weight is 1000-10000000; the molecular weight distribution is 1.1-3.5.
2. The cyclic olefin copolymer of claim 1, wherein the raw materials for preparing the cyclic olefin copolymer comprise 0.1-99.9 parts by weight of the styrenic monomer represented by formula (1), 0.1-99.9 parts by weight of the cyclic olefin monomer represented by formula (2) and/or formula (3), the catalyst represented by formula (4), and the cocatalyst;
3. The cycloolefin copolymer according to claim 2, characterized in that the cocatalyst is an aluminum alkyl and/or an alkylaluminoxane.
4. The cycloolefin copolymer according to claim 3, characterized in that the aluminum alkyl is selected from one or more of the group consisting of trimethylaluminum, triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum.
5. The cyclic olefin copolymer of claim 3, wherein the alkylaluminoxane is one or more selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
6. The ring of claim 2An olefin copolymer, characterized in that R is5、R6Each independently selected from any one of hydrogen, chlorine, bromine, methyl, ethyl, n-butyl, trifluoromethyl and tert-butyl; r7-12Each independently selected from any one of hydrogen, chlorine, bromine, methyl, ethyl, n-butyl, tert-butyl, isopropyl, trifluoromethyl, phenyl, p-methylphenyl, p-ethylphenyl, p-butylphenyl, methoxy, ethoxy, butoxy, phenoxy, dimethylamino, diethylamino, dibutylamino, dihexylamino, didecylamino, p-methylphenoxy and p-butylphenoxy; m is chromium or nickel; x1、X2Each independently selected from any one of chlorine, methyl, butyl, phenyl, benzyl and phenethyl.
7. The cycloolefin copolymer according to claim 2, wherein the styrenic monomer is selected from the group consisting of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 3-dimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,4,5, 6-pentamethylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2, 4-dimethoxystyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4, 6-trichlorostyrene, 2-methyl 4-chlorostyrene, 3-pentamethylstyrene, 6-pentamethylstyrene, 2-methoxystyrene, 4-dimethoxystyrene, 2-fluorostyrene, 4, 2, 6-dimethyl-4-chlorostyrene, 2-methoxy-4-chlorostyrene, 2, 6-dimethoxy-4-chlorostyrene.
8. The cycloolefin copolymer according to claim 2, wherein the cycloolefin monomer is selected from the group consisting of cyclopentene, cyclohexene, norbornene, 5-hydroxy-2-norbornene, 5-chloro-2-norbornene, 5-bromo-2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-methoxy-2-norbornene, 5-ethoxy-2-norbornene, 5-butoxy-2-norbornene, 5-hydroxymethyl-2-norbornene, 5-hydroxy-2-norbornene, 5-chloro-2-norbornene, 5-fluoro-2-norbornene, 5-, 5-hydroxyethyl-2-norbornene, 5-hydroxybutyl-2-norbornene, 5-carbomethoxy-2-norbornene, 5-carbethoxy-2-norbornene, 5-carbomethoxy-2-norbornene, tetracyclododecene, 9-hydroxytetracyclo-4-dodecene, 9-chlorotetracyclo-4-dodecene, 9-bromo-4-dodecene, 9-methyltetracyclo-4-dodecene, 9-ethyltetracyclo-4-dodecene, 9-butyltetracyclo-4-dodecene, 9-hexyltetracyclo-4-dodecene, 9-cyclohexyltetracyclo-4-dodecene, 9-methoxytetracyclo-4-dodecene, 2-hydroxynorbornene, 5-carbomethoxy-2-norbornene, 5-carbomethoxy-2, 9-ethoxy tetracyclo-4-dodecene, 9-butoxy tetracyclo-4-dodecene, 9-hydroxymethyl tetracyclo-4-dodecene, 9-hydroxyethyl tetracyclo-4-dodecene, 9-hydroxybutyl tetracyclo-4-dodecene, 9-carbomethoxytetracyclo-4-dodecene, 9-carbethoxytetracyclo-4-dodecene and 9-butyltetracyclo-4-dodecene.
9. The cyclic olefin copolymer according to any one of claims 1 to 8, wherein the starting materials for the preparation of the cyclic olefin further comprise a chain transfer agent selected from one or more of hydrogen, diethyl zinc, and aluminum alkyl.
10. A method for preparing a cycloolefin copolymer according to any one of claims 1 to 9, characterized in that it comprises: mixing the preparation raw materials of the cycloolefin copolymer, and reacting at 20-100 deg.C under 0.1-100 atm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989519A (en) * | 2022-06-09 | 2022-09-02 | 重庆理工大学 | Application of cycloolefin polymer in long afterglow material |
| CN114989519B (en) * | 2022-06-09 | 2023-08-25 | 重庆理工大学 | Application of cycloolefin polymer in long afterglow material |
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| CN112679642B (en) | 2023-05-12 |
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