CN116396478A - Preparation method of styrene thermoplastic polymer material - Google Patents
Preparation method of styrene thermoplastic polymer material Download PDFInfo
- Publication number
- CN116396478A CN116396478A CN202310193388.0A CN202310193388A CN116396478A CN 116396478 A CN116396478 A CN 116396478A CN 202310193388 A CN202310193388 A CN 202310193388A CN 116396478 A CN116396478 A CN 116396478A
- Authority
- CN
- China
- Prior art keywords
- initiator
- thermoplastic polymer
- polymer material
- lipoic acid
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002861 polymer material Substances 0.000 title claims abstract description 38
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229960002663 thioctic acid Drugs 0.000 claims abstract description 82
- 235000019136 lipoic acid Nutrition 0.000 claims abstract description 78
- 239000003999 initiator Substances 0.000 claims abstract description 76
- -1 aromatic olefin Chemical class 0.000 claims abstract description 53
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920005604 random copolymer Polymers 0.000 claims abstract description 23
- 230000000977 initiatory effect Effects 0.000 claims abstract description 21
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 claims abstract 10
- 239000000178 monomer Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000003960 organic solvent Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003839 salts Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 46
- 239000000243 solution Substances 0.000 abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 abstract description 16
- 229920001577 copolymer Polymers 0.000 abstract description 10
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract description 2
- AGBQKNBQESQNJD-UHFFFAOYSA-N lipoic acid Chemical compound OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000002091 cationic group Chemical group 0.000 description 12
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 10
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 238000007142 ring opening reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- NJXYTXADXSRFTJ-UHFFFAOYSA-N 1,2-Dimethoxy-4-vinylbenzene Chemical compound COC1=CC=C(C=C)C=C1OC NJXYTXADXSRFTJ-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RQHMQURGSQBBJY-UHFFFAOYSA-N (2,2-dichloroacetyl) 2,2-dichloroacetate Chemical compound ClC(Cl)C(=O)OC(=O)C(Cl)Cl RQHMQURGSQBBJY-UHFFFAOYSA-N 0.000 description 1
- PNVPNXKRAUBJGW-UHFFFAOYSA-N (2-chloroacetyl) 2-chloroacetate Chemical compound ClCC(=O)OC(=O)CCl PNVPNXKRAUBJGW-UHFFFAOYSA-N 0.000 description 1
- WRPYDXWBHXAKPT-UHFFFAOYSA-N (2-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1C=C WRPYDXWBHXAKPT-UHFFFAOYSA-N 0.000 description 1
- OWTJYMHZFCHOBI-UHFFFAOYSA-N (3-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=CC(C=C)=C1 OWTJYMHZFCHOBI-UHFFFAOYSA-N 0.000 description 1
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- NDTIXHNCNLKURN-UHFFFAOYSA-N (4-nitrophenyl) trifluoromethanesulfonate Chemical compound [O-][N+](=O)C1=CC=C(OS(=O)(=O)C(F)(F)F)C=C1 NDTIXHNCNLKURN-UHFFFAOYSA-N 0.000 description 1
- RJFYGCJTUUXOOF-UHFFFAOYSA-N (4-phenylphenyl) trifluoromethanesulfonate Chemical compound C1=CC(OS(=O)(=O)C(F)(F)F)=CC=C1C1=CC=CC=C1 RJFYGCJTUUXOOF-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- AGBQKNBQESQNJD-SSDOTTSWSA-N (R)-lipoic acid Chemical compound OC(=O)CCCC[C@@H]1CCSS1 AGBQKNBQESQNJD-SSDOTTSWSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 0.000 description 1
- PJKMOHIGRNELRP-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)benzene Chemical compound ClCC1=CC(CCl)=CC(CCl)=C1 PJKMOHIGRNELRP-UHFFFAOYSA-N 0.000 description 1
- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 description 1
- GRJWOKACBGZOKT-UHFFFAOYSA-N 1,3-bis(chloromethyl)benzene Chemical compound ClCC1=CC=CC(CCl)=C1 GRJWOKACBGZOKT-UHFFFAOYSA-N 0.000 description 1
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 1
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- IZXSWEQCVDBMOL-UHFFFAOYSA-N 1-(bromomethyl)-2-ethenylbenzene Chemical compound BrCC1=CC=CC=C1C=C IZXSWEQCVDBMOL-UHFFFAOYSA-N 0.000 description 1
- WFCJSNUJPWSKNE-UHFFFAOYSA-N 1-(bromomethyl)-3-ethenylbenzene Chemical compound BrCC1=CC=CC(C=C)=C1 WFCJSNUJPWSKNE-UHFFFAOYSA-N 0.000 description 1
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- SRXJYTZCORKVNA-UHFFFAOYSA-N 1-bromoethenylbenzene Chemical compound BrC(=C)C1=CC=CC=C1 SRXJYTZCORKVNA-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- WQDGTJOEMPEHHL-UHFFFAOYSA-N 1-chloro-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(Cl)C=C1 WQDGTJOEMPEHHL-UHFFFAOYSA-N 0.000 description 1
- CCSZEZULHZMGHK-UHFFFAOYSA-N 1-ethenyl-2-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=CC=C1C=C CCSZEZULHZMGHK-UHFFFAOYSA-N 0.000 description 1
- FIPBXQBXPNTQAA-UHFFFAOYSA-N 1-ethenyl-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1C=C FIPBXQBXPNTQAA-UHFFFAOYSA-N 0.000 description 1
- YNQXOOPPJWSXMW-UHFFFAOYSA-N 1-ethenyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C=C YNQXOOPPJWSXMW-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- VKVLTUQLNXVANB-UHFFFAOYSA-N 1-ethenyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=C VKVLTUQLNXVANB-UHFFFAOYSA-N 0.000 description 1
- ARHOUOIHKWELMD-UHFFFAOYSA-N 1-ethenyl-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C=C)=C1 ARHOUOIHKWELMD-UHFFFAOYSA-N 0.000 description 1
- LTGJSMARDKHZOY-UHFFFAOYSA-N 1-ethenyl-3-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=CC(C=C)=C1 LTGJSMARDKHZOY-UHFFFAOYSA-N 0.000 description 1
- LXOOIXRLEJSMKX-UHFFFAOYSA-N 1-ethenyl-3-ethoxybenzene Chemical compound CCOC1=CC=CC(C=C)=C1 LXOOIXRLEJSMKX-UHFFFAOYSA-N 0.000 description 1
- ZJSKEGAHBAHFON-UHFFFAOYSA-N 1-ethenyl-3-fluorobenzene Chemical compound FC1=CC=CC(C=C)=C1 ZJSKEGAHBAHFON-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 1
- CEWDRCQPGANDRS-UHFFFAOYSA-N 1-ethenyl-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C=C)C=C1 CEWDRCQPGANDRS-UHFFFAOYSA-N 0.000 description 1
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 description 1
- OBRYRJYZWVLVLF-UHFFFAOYSA-N 1-ethenyl-4-ethoxybenzene Chemical compound CCOC1=CC=C(C=C)C=C1 OBRYRJYZWVLVLF-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- LHJCZOXMCGQVDQ-UHFFFAOYSA-N tri(propan-2-yl)silyl trifluoromethanesulfonate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OS(=O)(=O)C(F)(F)F LHJCZOXMCGQVDQ-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- STMPXDBGVJZCEX-UHFFFAOYSA-N triethylsilyl trifluoromethanesulfonate Chemical compound CC[Si](CC)(CC)OS(=O)(=O)C(F)(F)F STMPXDBGVJZCEX-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention provides a preparation method of a styrene thermoplastic polymer material, which utilizes a cationic polymerization initiating system to initiate rigid aromatic olefin and flexible lipoic acid to carry out random copolymerization to obtain a random copolymer thermoplastic polymer material composed of aromatic olefin and lipoic acid, wherein the mole content of an aromatic olefin structural unit in the copolymer is 5-95%; the initiator system is various, the solution polymerization process is simple and safe to operate, a single-component initiator or a double-component initiator system consisting of an initiator and a co-initiator can be selected, the preparation is easy, the consumption is small, and the industrial production feasibility is realized; the polymerization can be carried out in the solution under the condition of low temperature or normal temperature; the thermoplastic polymer material of the random copolymer has repeatable hot workability and degradability in acidic or alkaline solution through disulfide bonds in lipoic acid chain links.
Description
Technical Field
The invention relates to a preparation method of a random copolymer thermoplastic high polymer material composed of aromatic olefin and lipoic acid. Belonging to the field of polymer material synthesis and preparation.
Background
Polystyrene and styrene copolymer are one of the six polymers produced and consumed, and commercial products including polystyrene plastics, styrenic thermoplastic elastomers, and the like, have been widely used in various fields of manufacturing tires, packaging materials, heat insulation materials, building materials, food processing, coatings, composite materials, and the like. However, the carbon-carbon bonds that make up their backbone make them difficult to degrade, resulting in their environmental durability, and limit the possibility of their recycling through chemical recovery or upgrading cycles, thus becoming one of the major sources of environmental pollution at present. The polystyrene thermoplastic material can be dissolved and recycled or reprocessed, and can also be directly thermally decomposed into molecular chain segments with low molecular weight, or (thermally/photo) catalytically decomposed to produce fuel-like products or recycled styrene monomer, or degraded into low molecular weight organic matters or mineralized into carbon dioxide by mixed microorganisms. The conversion of polystyrene into (bio) degradable material is also an effective solution to the contamination of polystyrene plastics. Copolymerization by introducing into the backbone a cyclic monomer capable of undergoing a ring-opening reaction with a vinyl monomer is an effective method of introducing cleavable bonds into the polymer backbone. Mudiyanelage et al have synthesized styrene-cinnamaldehyde copolymer films (Polym. Degrad. Stab.,2018,155,195-207) that are photodegradable under outdoor weathering conditions and under direct ultraviolet radiation by free radical copolymerization of styrene and cinnamaldehyde. Johnson and Guillainuf et al free-radically copolymerize styrene with a cyclothiolactone monomer, and degrade polystyrene by insertion of a thioester linkage of the polymer chain (Macromolecules, 2022,55 (15), 6680-6694; J.Am. Chem. Soc.,2022,144 (28), 12979-12988).
Lipoic acid (TA) is a cyclic disulfide naturally occurring in animals and having an antioxidant function, and has a molecular structure containing a cyclic disulfide bond and a carboxyl group. Lipoic acid can be synthesized into poly lipoic acid (Poly (thiocticacid), PTA) with dynamic disulfide bond in the main chain and carboxyl group in the side group through ring opening polymerization, and the linear polydisulfide can be depolymerized in a dilute solution of sodium hydroxide and reconverted into lipoic acid monomer, so that chemical ring closure recovery is realized (Matter, 2021,4 (4), 1352-1364), and the poly lipoic acid has biodegradability and is reduced and degraded into small molecules with biocompatibility through disulfide bond. The reaction of lipoic acid with other functionalized small molecules to consume the carboxylic derivatives can initiate anionic ring opening by free radical ring opening or thiol (salt), while lipoic acid can only be opened by free radical ring opening or cationic ring opening (J.Am. Chem. Soc.,2022,144 (5), 2022-2033; CN202211007010.9). Qu et al have free radical copolymerized lipoic acid with aromatic olefins, and metal chlorides under heating to produce dynamically reversible supramolecular polymers (Sci.Adv., 2018;4 (7), eaat8192; angew.chem.int.ed.,2020,59 (13), 5278-5283; CN202110366645.7).
The aromatic olefin such as styrene and lipoic acid can be subjected to cationic polymerization to prepare the corresponding polymer, however, the aromatic olefin and lipoic acid are combined into the same molecular chain through chemical bonds by cationic copolymerization, and no report is made so far. In particular, by copolymerizing aromatic olefin and lipoic acid, a thermally reversible disulfide bond which can be hydrolyzed and biodegradable under acidic or alkaline conditions is introduced into a polymer main chain, and simultaneously, a hydrogen bond is introduced into a carboxyl group of a side group of lipoic acid to carry out physical crosslinking, so that the performance of the material is enhanced.
Therefore, the random copolymer of the aromatic olefin and the lipoic acid is synthesized by utilizing a cationic polymerization method, the degradable styrene thermoplastic material is developed, and the preparation of the styrene thermoplastic plastic and the thermoplastic elastomer material can be realized by regulating the content of the lipoic acid monomer, so that the method has good application foundation and market prospect.
Disclosure of Invention
The invention aims to provide a preparation method of a styrene thermoplastic polymer material which can be repeatedly processed and degraded, and the invention can realize the efficient copolymerization of aromatic olefin and lipoic acid under the condition of the existence of a very small amount of initiating system to synthesize a random copolymer. The aromatic olefin and lipoic acid random copolymer polymer materials with different chemical compositions, different molecular weights and molecular weight distribution are synthesized by controlling the conditions of monomer concentration ratio, initiator concentration, polymerization reaction temperature, polymerization reaction time and the like, and the disulfide bonds in lipoic acid chain links in the main chain have thermal reversibility and are broken in alkaline solution to degrade the molecular chains, so that a brand-new preparation method of the styrene thermoplastic polymer materials capable of being repeatedly thermally processed and degraded is provided.
In order to solve at least one of the above problems, the present invention provides a method for preparing a styrenic thermoplastic polymer material, comprising:
adding an initiator into a reaction component according to a set molar ratio to obtain a mixed monomer component, wherein the reaction component is a mixture of an aromatic olefin monomer, a lipoic acid monomer and a first organic solvent, and the initiator can initiate the lipoic acid monomer to open a ring to form a positively charged sulfonium ion active center;
adding a reaction terminator into the mixed monomer reaction component added with the initiator to obtain an aromatic olefin and lipoic acid random copolymer;
and (3) drying the aromatic olefin and lipoic acid random copolymer to obtain the thermoplastic polymer material.
Preferably, the aromatic olefin monomer and the lipoic acid monomer are added to the first organic solvent in a set molar ratio, and the aromatic olefin monomer and the lipoic acid monomer are miscible in the organic solvent to obtain the reaction component.
Preferably, the preparation method of the styrenic thermoplastic polymer material further comprises the following steps:
and (3) dissolving the initiator in a second organic solvent according to a set molar ratio to obtain an initiator solution.
Preferably, a reaction terminator is added to the mixed monomer reaction component after the initiator is added to obtain the aromatic olefin and lipoic acid random copolymer.
Preferably, the initiator is a one-component initiator.
Preferably, the one-component initiator is a strong organic acid or an anhydride or ester corresponding to the strong organic acid.
Preferably, the initiator is a two-component initiator comprising a first initiator and a second initiator.
Preferably, the first initiator is a small molecule initiator with an active initiation site, and the second initiator is a salt or lewis acid corresponding to a strong organic acid.
Preferably, the preparation method of the styrenic thermoplastic polymer material further comprises the following steps:
the aromatic olefin monomer is styrene or polycyclic aromatic hydrocarbon or derivatives thereof.
Preferably, the reaction terminator is deionized water or an alkyl alcohol solution or a thiol solution.
The beneficial effects of the invention are that
The preparation method of the styrene thermoplastic polymer material provided by the invention utilizes the cationic polymerization initiation system to initiate the efficient copolymerization of the aromatic olefin and the lipoic acid, the initiation system is various, the aromatic olefin monomer has wide selection range, the solution polymerization process is simple, the operation is safe, and the bi-component initiation system consisting of single-component initiator or initiator and co-initiator can be selected, thus the preparation is easy, the consumption is small, and the industrial production feasibility is realized; the polymerization can be carried out in the solution under the condition of low temperature or normal temperature; the styrene thermoplastic polymer material is endowed with the repeatability and the degradability by introducing lipoic acid monomer capable of forming dynamic reversible disulfide bond in the main chain.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method of a styrene thermoplastic polymer material in an embodiment of the invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a copolymer obtained by copolymerizing lipoic acid and styrene cations induced by trifluoromethane sulfonic acid in an embodiment of the present invention.
Fig. 3 is a raman spectrum of a copolymer obtained by copolymerizing lipoic acid and styrene cations initiated by trifluoromethane sulfonic acid in an embodiment of the present invention.
FIG. 4 is a graph showing the elution profile of a copolymer obtained by copolymerizing lipoic acid and styrene cations initiated by trifluoromethane sulfonic acid according to an embodiment of the present invention, as measured by a gel permeation chromatograph.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
For convenience of description, the description of "first", "second", etc. in this application is provided for descriptive purposes only and is not to be construed as indicating or implying a relative importance or the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
Because the polystyrene is difficult to be chemically recovered and has environmental durability, the novel preparation method of the degradable styrene thermoplastic polymer material and the cationic copolymerization thereof has important practical application value.
Based on this, the invention provides a preparation method of a styrene thermoplastic polymer material, as shown in fig. 1, comprising the following steps:
step S101: adding an initiator into a reaction component according to a set molar ratio to obtain a mixed monomer component, wherein the reaction component is a mixture of an aromatic olefin monomer, a lipoic acid monomer and a first organic solvent, and the initiator can initiate the lipoic acid monomer to open a ring to form a positively charged sulfonium ion active center;
step S102: adding a reaction terminator into the mixed monomer reaction component added with the initiator to obtain an aromatic olefin and lipoic acid random copolymer;
step S103: and (3) drying the aromatic olefin and lipoic acid random copolymer to obtain the thermoplastic polymer material.
It is understood that the polymerization reaction that occurs by cationic initiation and formation of positively charged active sites during chain growth is referred to as cationic polymerization. The polymerization is a chain polymerization reaction, including elementary reactions such as chain initiation, chain extension and chain termination.
The lipoic acid has a simple structure, is a product of ring formation after 6-position hydrogen atoms and 8-position hydrogen atoms of the lipoic acid are replaced by mercapto groups, and contains cyclodisulfide bonds and carboxyl groups in the molecular structure of the lipoic acid. During the cationic polymerization reaction, the lipoic acid monomer opens to form a positively charged sulfonium ion active center. The lipoic acid has the following structure:
the aromatic olefin is vinyl monomer containing benzene ring, and is selected from styrene, alpha-methylstyrene, 4-fluoro-alpha-methylstyrene, 4-chloro-alpha-methylstyrene, beta-methylstyrene, alpha-bromostyrene, beta-bromostyrene, 2-methylstyrene, 3-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, alpha, 2-dimethylstyrene, 2, 5-dimethylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2-ethoxystyrene, 3-ethoxystyrene, 4-ethoxystyrene, 2-chloromethylstyrene, 3-chloromethylstyrene, 4-chloromethylstyrene, 2-bromomethylstyrene, 3-bromomethylstyrene, 4-bromomethylstyrene, 2-t-butoxystyrene, 3-t-butoxystyrene, 4-t-butoxystyrene, 2-acetoxystyrene, 3-acetoxystyrene, 4-acetoxystyrene, 2-nitrostyrene, 3-nitrostyrene, 4-nitrostyrene, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-fluorostyrene, 3-fluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, at least one of aromatic olefins such as 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 2-cyanostyrene, 3-cyanostyrene, 4-t-butylstyrene, 3- (trifluoromethyl) styrene, 4- (trifluoromethyl) styrene, 1, 2-divinylbenzene, 1, 3-divinylbenzene, 1, 4-divinylbenzene, allylbenzene, 4-allyltoluene, 3, 4-dimethoxystyrene, 3, 4-difluorostyrene, 2, 6-difluorostyrene, 4-phenoxystyrene, 1-diphenylethylene, 1, 2-diphenylethylene, N-dimethylaminostyrene, 2,4, 6-trimethylstyrene, 4-vinylbenzocyclobutene, 1-vinylnaphthalene, 1-allylnaphthalene, 2-isopropenylnaphthalene, and vinylanthracene and derivatives thereof.
The initiation system used in the method mainly comprises two types: one is directly initiated by super acid or corresponding ester thereof, the other is formed by a small molecular initiator with an active initiation site and salt or Lewis acid corresponding to the super acid as co-initiator, and the two initiation systems can initiate lipoic acid cation ring opening at low temperature or normal temperature to carry out homogeneous or heterogeneous polymerization. The invention can realize the efficient ring-opening polymerization of lipoic acid to synthesize the poly lipoic acid under the condition of the existence of a very small amount of initiating system. The polymer materials with different molecular weights and molecular weight distribution are synthesized by controlling the conditions of monomer concentration, initiator concentration, polymerization reaction temperature, polymerization reaction time and the like, and a brand-new ring-opening polymerization method for preparing the styrene thermoplastic materials is provided.
Dissolving lipoic acid and aromatic olefin monomer according to a molar ratio of 100 (1-10000) in a first organic solvent, adding an initiator, wherein the molar ratio of the monomer to the initiator is 5000 (1-100), dissolving lipoic acid and aromatic olefin monomer in the first organic solvent to obtain a total concentration of 0.1-10 mol/L, stirring for 5 min-4 h at low temperature or normal temperature, adding a precooled reaction terminator to stop polymerization reaction, removing initiator residues, and obtaining the lipoic acid and aromatic olefin random copolymer film after the solvent is completely volatilized; the reaction terminator may be any one of water, alkyl alcohol and alkyl mercaptan; the polymerization temperature of the cationic copolymerization of the lipoic acid and the aromatic olefin is-90-30 ℃, and the aromatic olefin and lipoic acid random copolymer is dried to obtain the thermoplastic polymer material.
As can be seen from the description, the preparation method of the styrene thermoplastic polymer material provided by the invention utilizes the cationic polymerization initiation system to initiate the efficient polymerization of lipoic acid and aromatic olefin, the initiation system is various, the solution polymerization process is simple, the operation is safe, and the preparation method can be used for preparing a single-component initiator or a dual-component initiation system consisting of an initiator and a co-initiator, is easy to prepare, has small consumption and has industrial production feasibility; the polymerization can be carried out in the solution under the condition of low temperature or normal temperature; the thermoplastic polymer material of the random copolymer has repeatable hot workability and degradability in acidic or alkaline solution through disulfide bonds in lipoic acid chain links.
In some embodiments, the method for preparing a styrenic thermoplastic polymer material further comprises:
dissolving the initiator in a second organic solvent according to a set molar ratio to obtain an initiator solution;
in the embodiment, the molar ratio of the lipoic acid to the aromatic olefin monomer is 100 (1-10000), the initiator is dissolved in the first organic solvent, the lipoic acid and the aromatic olefin mixed reaction component is introduced after the solution of the initiator is dissolved in the second organic solvent, the molar ratio of the monomer to the initiator is 5000 (1-100), the total concentration of the lipoic acid and the aromatic olefin monomer dissolved in the first organic solvent is 0.1-10 mol/L, the concentration of the initiator dissolved in the first or second organic solvent is 0.01-1 mol/L, the mixture is stirred at low temperature or normal temperature for 5 min-4 h, a precooled reaction terminator is added to terminate the polymerization reaction, the initiator residue is removed, and the lipoic acid and the aromatic olefin random copolymer film is obtained after the solvent is completely volatilized;
in some other embodiments, the initiator is a one-component initiator.
It will be appreciated that the one-component initiator is selected from the group consisting of trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, methyltrifluoromethanesulfonic acid, ethyltrifluoromethanesulfonic acid, propyltrifluoromethanesulfonic acid, butyltrifluoromethanesulfonic acid, allyltrifluoromethanesulfonic acid, benzyltrifluoromethanesulfonic acid, o-tolylsulfonate, 4-biphenyltriflate, 4-nitrophenyl trifluoromethanesulfonate, difluoromethyl trifluoromethanesulfonate, 2-difluoroethyl trifluoromethanesulfonate, trimethylsilyl trifluoromethanesulfonate, triethylsilyl trifluoromethanesulfonate, triisopropylsilyl trifluoromethanesulfonate, trifluoroacetic acid, trifluoroacetic anhydride, butyltrifluoromethaneacrylate, trichloroacetic acid, dichloroacetic anhydride, chloroacetic acid anhydride, p-toluenesulfonic acid, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, perchloric acid, boric acid esters, fluoroboric acid and the like, and ester derivatives thereof, strong acid ion exchange resins such as perfluorosulfonic acid resin, high concentration heteropolyacid such as phosphotungstic acid, aluminum phosphotungstate, iron phosphotungstate, potassium phosphotungstate, sodium phosphotungstate, and the like, and salts thereof, and at least one of metal oxide solid superacids such as iron base, aluminum base, zirconium base, chromium base, titanium base, molybdenum base, dysprosium base, and the like.
In some embodiments, the initiator is a two-component initiator comprising a first initiator that is a small molecule initiator with an active initiation site and a second initiator that is a salt or lewis acid corresponding to a strong organic acid.
It will be appreciated that the initiator in the two-component initiation system is selected from at least one of allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, benzyl chloride, benzyl bromide, α -dimethylbenzyl chloride, α -dimethylbenzyl bromide, 1, 3-di (chloromethyl) benzene, 1, 3-di (bromomethyl) benzene, 1, 4-di (chloromethyl) benzene, 1, 4-di (bromomethyl) benzene, 1,3, 5-tri (chloromethyl) benzene, 1,3, 5-tri (bromomethyl) benzene, methacryloyl chloride, methacryloyl bromide;
the co-initiator in the two-component initiation system is selected from silver fluorosulfonate, silver trifluoromethanesulfonate, triflate of lanthanoid elements (yttrium, scandium, dysprosium, samarium, gadolinium and neodymium), silver hexafluorophosphate, silver hexafluoroarsenate, and hexaSilver fluoroantimonate, lithium perchlorate, potassium perchlorate, manganese perchlorate, silver perchlorate, magnesium perchlorate, calcium perchlorate, cesium perchlorate, barium perchlorate, iron perchlorate and the like, zinc dichloride, cadmium dichloride, mercury dichloride, aluminum trichloride, aluminum tribromide, gallium trichloride, iron trichloride, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, vanadium tetrachloride, antimony pentafluoride, antimony pentachloride, antimony hexafluoride, tungsten pentachloride, boron trichloride, boron trifluoride, boron tribromide, alR m X 3-m (R is alkyl such as methyl or ethyl, and X is halogen) and the like.
In some specific embodiments, the first and second organic solvents are each selected from at least one of methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, N-hexane, cyclohexane, N-heptane, tetrahydrofuran, acetone, butanone, diethyl ether, acetonitrile, benzonitrile, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane.
When the initiating system can be dissolved in the first or the second organic solvent, the polymerization reaction is homogeneous polymerization reaction; when the one-component initiator is insoluble in the first or second organic solvent, the polymerization is a heterogeneous polymerization.
The present application is described in detail below by way of specific examples.
Example 1
1g (4.85 mmol) of lipoic acid powder was weighed into a small polymerization bottle which had been dehydrated by heating beforehand, 20mL of methylene chloride which had been dehydrated beforehand was added to the small polymerization bottle, 0.56mL (4.85 mmol) of styrene was added thereto, the bottle mouth was sealed, and the small polymerization bottle was placed in an ice-water bath at 0℃for 1 hour, and stirred while being dissolved. To a small polymerization flask was added 10. Mu.L (0.0125 mmol) of trifluoromethanesulfonic acid (molar ratio of lipoic acid to styrene two monomers to trifluoromethanesulfonic acid initiator 776:1) with a microsyringe, and the reaction was continued with stirring for 2 hours. And adding precooled propanethiol to terminate the polymerization reaction, namely finishing the cationic copolymerization reaction process of the lipoic acid and the styrene, and fully drying to obtain the styrene-lipoic acid random copolymer.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a copolymer obtained by cationic copolymerization of lipoic acid and styrene initiated by trifluoromethane sulfonic acid in example 1, and it can be seen from the graph that the lipoic acid monomer and the styrene monomer are subjected to cationic copolymerization to form a random copolymer, and the molar content of the styrene structure is 9% through integral calculation; FIG. 3 is a Raman spectrum of a copolymer obtained by copolymerizing lipoic acid and styrene cations induced by trifluoromethane sulfonic acid in example 1, and shows that, due to the ring opening of lipoic acid monomers, copolymerization is carried out with styrene, cyclodisulfide bonds are converted into linear disulfide bonds, and vibration peaks of carbon-carbon bonds in a styrene structural unit appear at the same time; FIG. 4 is a graph showing the elution profile of the copolymer obtained by copolymerizing lipoic acid and styrene cations induced by trifluoromethane sulfonic acid in example 1, wherein the copolymer obtained by copolymerizing lipoic acid and styrene cations has a number average molecular weight of 37600 and a molecular weight distribution index of 1.78, and is unimodal.
Examples 2 to 4
The remaining steps and conditions of the polymerization were the same as in example 1 except that the molar ratio of lipoic acid to styrene was changed, as shown in Table 1:
TABLE 1
Examples 5 to 8
The procedure and conditions for the polymerization were the same as in example 1 except that the polymerization temperature was changed, and are specifically shown in Table 2:
TABLE 2
| Sequence number | Polymerization temperature |
| Example 5 | 25℃ |
| Example 6 | -15℃ |
| Example 7 | -50℃ |
| Example 8 | -80℃ |
Example 9
0.5g (2.42 mmol) of lipoic acid powder is weighed and placed in a small polymerization bottle which is preheated to remove water, 20mL of toluene which is preheated to remove water is added into the small polymerization bottle, 0.28mL (2.42 mmol) of styrene is added into the small polymerization bottle, a bottle opening is sealed, and the small polymerization bottle is placed in an ice-water bath at 0 ℃ to be precooled for 1 hour, and is stirred to be dissolved. 2. Mu.L (0.0025 mmol) of trifluoromethanesulfonic acid was added to the small polymerization flask by a microsyringe, and the reaction was continued with stirring for 2 hours. And adding precooled propanethiol to terminate the polymerization reaction, namely finishing the cationic copolymerization reaction process of the lipoic acid and the styrene, and fully drying to obtain the styrene-lipoic acid random copolymer.
Example 10
0.5g (2.42 mmol) of lipoic acid powder was weighed into a small polymerization bottle which had been dehydrated by heating in advance, 10mL of toluene which had been dehydrated in advance was added to the small polymerization bottle, 0.28mL (2.42 mmol) of styrene was added thereto, 4. Mu.L (0.0457 mmol) of allyl bromide was added to the small polymerization bottle with a microsyringe, the bottle mouth was sealed, and the small polymerization bottle was placed in an ice-water bath at 0℃for precooling for 1 hour while stirring to dissolve. 10mg (0.048 mmol) of silver perchlorate is weighed and dissolved in 10mL of toluene which has been dehydrated beforehand, and placed in another single-necked vial which has been dehydrated by heating beforehand, and then the toluene solution of silver perchlorate in the single-necked vial is added to the vial, and the reaction is continued with stirring for 2 hours. And adding precooled propanethiol to terminate the polymerization reaction, namely finishing the cationic copolymerization reaction process of the lipoic acid and the styrene, and fully drying to obtain the styrene-lipoic acid random copolymer.
Example 11
0.5g (2.42 mmol) of lipoic acid powder was weighed into a small polymerization bottle which had been dehydrated by heating in advance, 10mL of toluene which had been dehydrated in advance was added to the small polymerization bottle, 0.28mL (2.42 mmol) of styrene was added thereto, 5. Mu.L (0.0421 mmol) of benzyl bromide was added to the small polymerization bottle by a microsyringe, the bottle mouth was sealed, and the small polymerization bottle was placed in an ice-water bath at 0℃for precooling for 1 hour while stirring to dissolve. 8mg (0.048 mmol) of ferric trichloride is weighed and dissolved in 10mL of acetone which is dehydrated in advance, the mixture is placed in another single-port small bottle which is dehydrated in advance by heating, then an acetone solution of the ferric trichloride in the single-port small bottle is added into a small polymerization bottle, and the reaction is continued for 2 hours under stirring. And adding precooled propanethiol to terminate the polymerization reaction, namely finishing the cationic copolymerization reaction process of the lipoic acid and the styrene, and fully drying to obtain the styrene-lipoic acid random copolymer.
Examples 12 to 17
The rest of the polymerization reaction and conditions were the same as in example 1 except that the kind of aromatic olefin monomer was changed, as specifically shown in Table 3:
TABLE 3 Table 3
From the above description, the invention discloses a preparation method of a styrene thermoplastic polymer material, which is selected from a method for performing homogeneous or heterogeneous polymerization by initiating cationic copolymerization of lipoic acid and styrene monomer by low-temperature or normal-temperature solution; the cationic polymerization system used in the method of the invention has the advantages of multiple types, simple solution polymerization process, safe operation, easy preparation, small consumption, high polymerization efficiency and industrial production feasibility, and can select a single-component initiator or a two-component initiator system consisting of an initiator and a co-initiator; the polymerization may be carried out either homogeneously or heterogeneously in a solution at low or normal temperature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present specification. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example.
Furthermore, the various embodiments or examples described in this specification and the features of the various embodiments or examples may be combined and combined by those skilled in the art without contradiction. The above description is merely an embodiment of the present specification and is not intended to limit the present specification. Various modifications and changes may be made to the embodiments herein by those skilled in the art. Any modification, equivalent replacement, improvement, or the like, which is made within the spirit and principle of the embodiments of the present specification, should be included in the scope of the claims of the embodiments of the present specification.
Claims (10)
1. The preparation method of the styrene thermoplastic polymer material is characterized by comprising the following steps:
adding an initiator into a reaction component according to a set molar ratio to obtain a mixed monomer component, wherein the reaction component is a mixture of an aromatic olefin monomer, a lipoic acid monomer and a first organic solvent, and the initiator can initiate the lipoic acid monomer to open a ring to form a positively charged sulfonium ion active center;
adding a reaction terminator into the mixed monomer reaction component added with the initiator to obtain an aromatic olefin and lipoic acid random copolymer;
and (3) drying the aromatic olefin and lipoic acid random copolymer to obtain the thermoplastic polymer material.
2. The method for producing a styrenic thermoplastic polymer material according to claim 1, wherein the method for producing a styrenic thermoplastic polymer material further comprises:
and adding the aromatic olefin monomer and the lipoic acid monomer into the first organic solvent according to a set molar ratio, wherein the aromatic olefin monomer and the lipoic acid monomer are mixed and dissolved in the organic solvent, so as to obtain the reaction component.
3. The method for producing a styrenic thermoplastic polymer material according to claim 1, wherein the method for producing a styrenic thermoplastic polymer material further comprises:
and (3) dissolving the initiator in a second organic solvent according to a set molar ratio to obtain an initiator solution.
4. The method for preparing a styrene thermoplastic polymer according to claim 1, wherein a reaction terminator is added to the mixed monomer reaction component after the addition of the initiator to obtain a random copolymer of aromatic olefin and lipoic acid.
5. The method for producing a styrenic thermoplastic polymer according to claim 1, wherein the initiator is a one-component initiator.
6. The method for preparing a styrene thermoplastic polymer material according to claim 5, wherein the single-component initiator is a strong organic acid or an anhydride or ester corresponding to the strong organic acid.
7. The method for preparing a styrene thermoplastic polymer material according to claim 1, wherein the initiator is a two-component initiator comprising a first initiator and a second initiator.
8. The method for preparing a styrene thermoplastic polymer material according to claim 7, wherein the first initiator is a small molecular initiator with an active initiation site, and the second initiator is a salt or lewis acid corresponding to a strong organic acid.
9. The method for producing a styrenic thermoplastic polymer material according to claim 1, wherein the method for producing a styrenic thermoplastic polymer material further comprises:
the aromatic olefin monomer is styrene or polycyclic aromatic hydrocarbon or derivatives thereof.
10. The method for preparing a styrene thermoplastic polymer material according to claim 1, wherein the reaction terminator is deionized water or an alkyl alcohol solution or a thiol solution.
Priority Applications (1)
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