CN109337059B - 一种以噻唑鎓盐为催化剂的环酯本体开环聚合方法及催化剂制备方法 - Google Patents
一种以噻唑鎓盐为催化剂的环酯本体开环聚合方法及催化剂制备方法 Download PDFInfo
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- CN109337059B CN109337059B CN201811038667.5A CN201811038667A CN109337059B CN 109337059 B CN109337059 B CN 109337059B CN 201811038667 A CN201811038667 A CN 201811038667A CN 109337059 B CN109337059 B CN 109337059B
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- thiazolium
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- ring
- opening polymerization
- cyclic ester
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- -1 cyclic ester Chemical class 0.000 title claims abstract description 56
- 150000003839 salts Chemical class 0.000 title claims abstract description 48
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000008282 halocarbons Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003254 radicals Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- KAESVJOAVNADME-UHFFFAOYSA-O hydron;1h-pyrrole Chemical compound [NH2+]1C=CC=C1 KAESVJOAVNADME-UHFFFAOYSA-O 0.000 abstract description 10
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 69
- 238000001914 filtration Methods 0.000 description 59
- 239000000047 product Substances 0.000 description 52
- 239000002244 precipitate Substances 0.000 description 50
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 46
- 238000003756 stirring Methods 0.000 description 46
- 238000001035 drying Methods 0.000 description 38
- 238000010438 heat treatment Methods 0.000 description 31
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 28
- 239000000706 filtrate Substances 0.000 description 23
- 238000005227 gel permeation chromatography Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 229920001610 polycaprolactone Polymers 0.000 description 21
- 239000004632 polycaprolactone Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- 238000007789 sealing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 9
- 229960000344 thiamine hydrochloride Drugs 0.000 description 9
- 235000019190 thiamine hydrochloride Nutrition 0.000 description 9
- 239000011747 thiamine hydrochloride Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 239000000622 polydioxanone Substances 0.000 description 3
- JZRWCGZRTZMZEH-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KRPUXJPMHKGIRZ-UHFFFAOYSA-M 3-benzyl-1,3-benzothiazol-3-ium;bromide Chemical compound [Br-].C=1SC2=CC=CC=C2[N+]=1CC1=CC=CC=C1 KRPUXJPMHKGIRZ-UHFFFAOYSA-M 0.000 description 2
- RNNHDVNXKHLIKX-UHFFFAOYSA-M 3-benzyl-4-methyl-1,3-thiazol-3-ium;bromide Chemical compound [Br-].CC1=CSC=[N+]1CC1=CC=CC=C1 RNNHDVNXKHLIKX-UHFFFAOYSA-M 0.000 description 2
- MRTFKXMJTGPNDA-UHFFFAOYSA-M 3-ethyl-4-methyl-1,3-thiazol-3-ium;bromide Chemical compound [Br-].CC[N+]1=CSC=C1C MRTFKXMJTGPNDA-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 2
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 description 1
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- QUAMMXIRDIIGDJ-UHFFFAOYSA-N 5-ethenyl-4-methyl-1,3-thiazole Chemical compound CC=1N=CSC=1C=C QUAMMXIRDIIGDJ-UHFFFAOYSA-N 0.000 description 1
- PBFHCNBIJXCPQZ-UHFFFAOYSA-N CCN1C(C)=C(CCO)SC1.Br Chemical compound CCN1C(C)=C(CCO)SC1.Br PBFHCNBIJXCPQZ-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- SHAPNCDSULSPRT-UHFFFAOYSA-M sodium 2-hydroxyhexanoate Chemical compound OC(C(=O)[O-])CCCC.[Na+] SHAPNCDSULSPRT-UHFFFAOYSA-M 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 229960002363 thiamine pyrophosphate Drugs 0.000 description 1
- 235000008170 thiamine pyrophosphate Nutrition 0.000 description 1
- 239000011678 thiamine pyrophosphate Substances 0.000 description 1
- YXVCLPJQTZXJLH-UHFFFAOYSA-N thiamine(1+) diphosphate chloride Chemical compound [Cl-].CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N YXVCLPJQTZXJLH-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/24—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明提供了一种用噻唑鎓盐作为催化剂的环酯本体开环聚合方法，并提供了所述的噻唑鎓盐催化剂的制备方法。本发明通过离子交换调整噻唑鎓的阴离子，使得噻唑鎓盐催化剂能溶于环酯单体，并实现对环酯本体开环聚合良好的催化作用。本发明提供的方法实现了将唑鎓直接用于催化开环聚合，而不需要拔氢再制备为氮杂环卡宾，因此，相对于现有技术中将噻唑鎓拔氢制备的另一类催化剂——噻唑卡宾，本发明提供的噻唑鎓催化剂对水和氧气的稳定性更好，制备更简单，且绿色环保、易于稳定储存与使用；且本发明提供的催化环酯本体开环聚合适用于多种单体，催化效率适中，催化温度窗口宽，可明显提高环酯开环聚合、聚酯制备的可工业应用程度。
Description
技术领域
本发明属于催化开环聚合技术领域，具体涉及将一种无金属催化剂用作催化环酯开环聚合的方法。
背景技术
催化环酯开环聚合是制备聚乳酸、聚己内酯、聚对二氧环己酮、聚戊内酯、聚碳酸酯等聚酯的典型方法。这类聚酯由于其优良的生物相容性和降解性能使其被广泛应用到生物医疗方面。因此，对开环聚合催化剂的残留与毒性有严格的限制。传统开环聚合催化剂多为金属配合物，其金属离子往往具有毒性且难以去除，使其在生物医疗应用中受限。众多金属配合物催化剂(有机锡类、有机铝类、有机锌类、稀土配合物类)中，仅有辛酸亚锡通过了美国食品药品监督管理局(FDA)认证。使用金属配合物催化环酯单体开环聚合得到的产物，需经过严格的后处理以避免金属离子残留量超过标准，使得其成本高昂。
本世纪以来，“无金属(metal-free)”催化剂因为较易于从产物中去除，在开环聚合催化领域得到提倡，更多的研发了有机催化剂(如专利CN201710243019.2)。在氮杂环这一大类化合物中，已有多种结构可催化开环聚合，如4-二甲氨基吡啶(DMAP)、1,8-二氮杂二环十一碳-7-烯(DBU)等。其中，五元共轭氮杂环包括咪唑、噻唑、三氮唑等唑类，及咪唑鎓、噻唑鎓、三氮唑鎓等唑鎓类，以及咪唑卡宾、噻唑卡宾、三氮唑卡宾等氮杂环卡宾类(NHCs)；几类化合物间可相互转换，唑类的氮取代可制备唑鎓，唑鎓拔氢可制备氮杂环卡宾，氮杂环卡宾加氢可制备唑鎓。唑类中，利用其氮杂环氮上氢的活性，已可将其作为开环聚合催化剂(如专利CN201710285930.X)。氮杂环卡宾类中，各种氮杂环卡宾在催化开环聚合应用中均已受到了较为全面的研究，其中咪唑卡宾、三氮唑卡宾有极高的催化效率。文章(Journalofthe American Chemical Society,2003,125:3046-56)中成功将包括硫胺素(VB1)在内的噻唑鎓盐用三乙胺拔氢，制备成为噻唑类卡宾用作催化环酯开环聚合。但是，在用作催化环酯开环聚合中，噻唑类卡宾催化效率较低，并同样具有氮杂环卡宾共同的缺陷——对水、氧气极为敏感。氮杂环卡宾制备条件较为严苛，稳定性不足；而较易制备、较为稳定的唑鎓类又尚不能催化开环聚合。
因此，研发一种将唑鎓直接用于催化开环聚合的，具有绿色、稳定、制备方法简单、易于稳定储存与使用的优点的方法，能够克服现有技术中存在的问题，提高环酯开环聚合、聚酯制备的可工业应用程度。
发明内容
本发明针对现有技术中存在的缺陷，提供了一种用噻唑鎓盐作为催化剂的环酯本体开环聚合方法，并提供了所述的噻唑鎓盐催化剂的制备方法。本发明通过离子交换调整噻唑鎓的阴离子，使得噻唑鎓盐催化剂能溶于环酯单体，并实现对环酯本体开环聚合良好的催化作用。
本发明提供的方法实现了将唑鎓直接用于催化开环聚合，而不需要拔氢再制备为氮杂环卡宾，因此，相对于现有技术中将噻唑鎓拔氢制备的另一类催化剂——噻唑卡宾，本发明提供的噻唑鎓催化剂对水和氧气的稳定性更好，制备更简单，且绿色环保、易于稳定储存与使用；且本发明提供的催化环酯本体开环聚合适用于多种单体，催化效率适中，催化温度窗口宽。
本发明是通过以下技术方案实现的：
一种以噻唑鎓盐为催化剂的环酯本体开环聚合方法，以噻唑鎓盐作为催化剂，以水或者含羟基化合物作为引发剂，催化环酯本体开环聚合，得到聚酯。
进一步地，所述的噻唑鎓盐的结构式为(Ⅰ):
其中，噻唑鎓部分的结构特征为：噻唑环上2-位碳上含氢，3-位氮上接R1基团，4、5-位碳上接R2、R3基团，其中R1、R2、R3选自任意基团；阴离子X为小分子阴离子、聚阴离子或被固载的阴离子中的一种或几种。
进一步地，所述的阴离子X为Tf2N-，PF6 -，BF4 -，AlnCl3n+1 -，R-COO-，带羧酸根聚合物、被固载的羧酸根，R-SO3 -，带磺酸根聚合物、或被固载的磺酸根，F-，Cl-，Br-，I-，NO3 -，SO4 2-，H2PO4 -中的一种或几种。其中小分子阴离子为Tf2N-，PF6 -，BF4 -，AlnCl3n+1 -，R-COO-，R-SO3 -，F-，Cl-，Br-，I-，NO3 -，SO4 2-，H2PO4 -；聚阴离子为带羧酸根聚合物，带磺酸根聚合物；被固载的阴离子为被固载的羧酸根，被固载的磺酸根。
进一步地，所述的阴离子X优选PF6 -与R-SO3 -、聚丙烯酸根、聚苯乙烯磺酸根及磺酸型与丙烯酸型离子交换树脂。其中PF6 -与R-SO3 -为小分子阴离子；聚丙烯酸根、聚苯乙烯磺酸根为聚阴离子；磺酸型与丙烯酸型离子交换树脂为被固载阴离子。
进一步地，所述的噻唑鎓部分为小分子噻唑鎓，或聚合的噻唑鎓，或被负载的噻唑鎓，或被复配的噻唑鎓。
进一步地，所述的噻唑鎓为小分子噻唑鎓时，所述的噻唑鎓盐优选结构式为(Ⅱ)、(Ⅲ)、(Ⅳ)、(Ⅴ)、(Ⅵ)；所述的噻唑鎓部分为聚合的、被负载的或者被复配的噻唑鎓时，所述的噻唑鎓盐优选结构式为(Ⅶ)，其中n表示聚合物聚合单元数，聚合单元数不限。
其中结构为(Ⅱ)、(Ⅲ)的噻唑鎓盐可进一步优选结构为(XII)与(XIII)。
进一步地，所述的被催化的环酯单体结构式为环内酯(Ⅷ)、环交酯(Ⅸ)、环碳酸酯(Ⅹ)和环酯-醚(Ⅺ)中的一种或几种，其中R4、R6选自氢或具有1～5个碳原子的烷基，R5选自氢或甲基，R7选自氢或羟甲基，m1、m2表示重复单元数量为1～4。
进一步地，所述的环酯单体与所述的噻唑鎓盐催化剂的投料摩尔比为10-1000/1；所述方法的反应温度为60-180℃。
进一步地，所述的开环聚合得到的聚酯分子量为1000-100000g/mol、分子量分布为1.05-2.00。
一种噻唑鎓盐催化剂的制备方法，包括以下步骤：
(1)将噻唑类化合物与卤代烃以摩尔比1:1投料，在无溶剂或者以乙酸乙酯为溶剂下20-80℃反应0.5-72h，得到的产物用乙酸乙酯多次清洗，得到的噻唑鎓盐为初始噻唑鎓盐；再对其中含有不饱和基团的初始噻唑鎓盐进行自由基聚合，得到的为初始聚噻唑鎓盐；此外，所述的初始噻唑鎓盐也可从现有工业产品直接获取。
(2)将步骤(1)中制备得到的所述初始噻唑鎓盐、初始聚噻唑鎓盐与含有阴离子X的盐在水或醇中，通过复分解反应或浓缩结晶实现阴离子部分的交换，得到阴阳离子优配后的噻唑鎓盐，即所述的用作催化剂的噻唑鎓盐，所述的催化剂在水或者醇中不溶或者溶解度较低。
进一步地，步骤(1)中所述的噻唑类化合物为噻唑、4-取代噻唑、5-取代噻唑或者4,5-二取代噻唑；所述卤代烃包括溴乙烷、氯丙醇、卞溴或者二苯甲溴。所述初始噻唑鎓盐的初始聚噻唑鎓部分结构为(Ⅱ)、(Ⅲ)、(Ⅳ)、(Ⅴ)、(Ⅵ)、(Ⅶ)中的一种或几种，当中(Ⅱ)、(Ⅲ)可从工业产品直接获取或由卤代烃取代制备，(Ⅳ)、(Ⅴ)、(Ⅵ)、(Ⅶ)需卤代烃取代，(Ⅶ)还需由噻唑环5-位乙烯基自由基聚合得到。
本发明实现了如下有益效果：
(1)制备的噻唑鎓盐催化剂结构明确，易溶或者可溶于环酯单体、有良好催化能力，催化剂化学性质稳定、易于保存与使用。
(2)将噻唑鎓盐用作环酯开环聚合反应催化剂，催化过程可实现本体聚合、无需溶剂，反应条件对水、氧气、pH无严苛要求；催化效率良好，在12h内可达到99％以上的单体转化率；可实现对己内酯、戊内酯、对二氧环己酮等多种环酯单体的开环聚合。
具体实施例
下面给出的实施例是为了说明本发明，而不是对本发明进行限制。实施例中所制备和使用催化剂的结构式如表1所示。
表1：实施例中噻唑鎓盐催化剂结构式一览表
实施例1：
将3.37g盐酸硫胺溶于5ml水、配为溶液A，将0.40g氢氧化钠溶于2ml水、配为溶液B，将2.87g双三氟甲烷磺酰亚胺锂溶于2ml水、配为溶液C；混合A、B溶液，充分搅拌后，使盐酸硫胺中的盐酸基本被中和掉；再向A、B混合溶液中加入溶液C，充分搅拌后静置至沉淀完全；过滤，烘干，得到白色粉末状固体i。
以i作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.137g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率96％，产物由氯仿相凝胶渗透色谱测得相对数均分子量10400g/mol，分子量分布1.24。
实施例2：
将3.37g盐酸硫胺溶于5ml、水配为溶液A，将0.40g氢氧化钠溶于2ml、水配为溶液B，将1.68g六氟磷酸钠溶于2ml、水配为溶液C；混合A、B溶液，充分搅拌后，使盐酸硫胺中的盐酸基本被中和掉；再向A、B混合溶液中加入溶液C，充分搅拌后静置至沉淀完全；过滤，烘干，得到白色粉末状固体ii。
以ii作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.103g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率99％，产物由氯仿相凝胶渗透色谱测得相对数均分子量32600g/mol，分子量分布1.27。
实施例3：
将3.37g盐酸硫胺溶于5ml、水配为溶液A，将0.40g氢氧化钠溶于2ml、水配为溶液B，将1.10g四氟硼酸钠溶于2ml、水配为溶液C；混合A、B溶液，充分搅拌后，使盐酸硫胺中的盐酸基本被中和掉；再向A、B混合溶液中加入溶液C，充分搅拌后静置至沉淀完全；过滤，烘干，得到白色粉末状固体iii。
以iii作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.088g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率99％，产物由氯仿相凝胶渗透色谱测得相对数均分子量11800g/mol，分子量分布1.21。
实施例4：
将3.37g盐酸硫胺溶于3.40ml二次水，再将1.90g一水合对甲苯磺酸溶于其中，充分搅拌后静置48h，结晶析出部分白色固体；过滤，烘干，得到白色粉末状固体iv。
以iv作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.088g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率83％，产物由氯仿相凝胶渗透色谱测得相对数均分子量7700g/mol，分子量分布1.15。
实施例5：
将3.37g盐酸硫胺溶于3.40ml二次水，再将3.08g羟基己酸钠溶于其中，充分搅拌后静置48h，结晶析出部分白色固体；过滤，烘干，得到白色粉末状固体v。
以v作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.088g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率79％，产物由氯仿相凝胶渗透色谱测得相对数均分子量6700g/mol，分子量分布1.16。
实施例6：
将17.1g卞溴和8.50g噻唑溶于30ml乙酸乙酯中，加热回流48h后产生大量白色沉淀，停止加热，冷却室温后过滤出白色粉末状固体，用乙酸乙酯多次清洗后烘干，得3-苄基噻唑鎓溴。
将2.56g合成的3-苄基噻唑鎓溴溶于10ml水，将2.87g双三甲烷磺酰亚胺锂加入其水溶液中，充分搅拌后静置至沉淀完全。过滤，取固体烘干，制得vi。
以vi作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.122g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率92％，产物由氯仿相凝胶渗透色谱测得相对数均分子量12600g/mol，分子量分布1.28。
实施例7：
将12.5g 4-甲基-5-乙烯基噻唑与17.1g卞溴共溶于30ml乙酸乙酯中，75℃油浴条件下充分搅拌24h，析出白色固体4-甲基-3-苄基-5-乙烯基噻唑溴鎓。再在水溶液中以过硫酸铵为引发剂(单体与引发剂摩尔比100/1)，75℃油浴、密封体系中反应24h；反应结束后对反应液做透析处理，再向其透析后水溶液中加入过量双三氟甲烷磺酰亚胺锂，得到固体产物vii。
以vii作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.125g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率84％，产物由氯仿相凝胶渗透色谱测得相对数均分子量8400g/mol，分子量分布1.31。
实施例8：
将4.61g焦磷酸硫胺溶于10ml、水配为溶液A，将2.87g双三氟甲烷磺酰亚胺锂溶于2ml、水配为溶液B；混合A、B溶液，充分搅拌后静置至沉淀完全；过滤，烘干，得到白色粉末状固体viii。
以viii作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.177g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率72％，产物由氯仿相凝胶渗透色谱测得相对数均分子量6300g/mol，分子量分布1.34。
实施例9：
将2.52g 3-乙基-5-(2-羟乙基)-4-甲基噻唑溴盐溶于5m、水配为溶液A，将2.87g双三甲烷磺酰亚胺锂溶于2ml、水配为溶液B；混合A、B液，充分搅拌后静置至分液完全，得到下层黄色透明不水溶的离子液体；分液，取下层黄色离子液体烘干，得到ix。
以ix作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.131g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率80％，产物由氯仿相凝胶渗透色谱测得相对数均分子量7600g/mol，分子量分布1.19。
实施例10：
将10.9g溴乙烷和9.9g 4-甲基噻唑溶于30ml乙酸乙酯中，加热回流48h后产生大量白色沉淀，停止加热，冷却室温后过滤出白色粉末状固体，用乙酸乙酯多次清洗后烘干，得3-乙基-4-甲基噻唑鎓溴。
将2.08g合成的3-乙基-4-甲基噻唑鎓溴溶于10ml水，将2.87g双三甲烷磺酰亚胺锂加入其水溶液中，充分搅拌后静置至沉淀完全。过滤，取固体烘干，制得x。
以x作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.112g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率92％，产物由氯仿相凝胶渗透色谱测得相对数均分子量12600g/mol，分子量分布1.28。
实施例11：
将17.1g溴化苄和9.9g 4-甲基噻唑溶于30ml乙酸乙酯中，加热回流48h后产生大量白色沉淀，停止加热，冷却室温后过滤出白色粉末状固体，用乙酸乙酯多次清洗后烘干，得3-苄基-4-甲基噻唑鎓溴。
将2.70g合成的3-苄基-4-甲基噻唑鎓溴溶于10ml水，将2.87g双三甲烷磺酰亚胺锂加入其水溶液中，充分搅拌后静置至沉淀完全。过滤，取固体烘干，制得xi。
以xi作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.121g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率89％，产物由氯仿相凝胶渗透色谱测得相对数均分子量11300g/mol，分子量分布1.22。
实施例12：
将17.1g溴化苄和13.5g苯并噻唑溶于30ml乙酸乙酯中，加热回流48h后产生大量白色沉淀，停止加热，冷却室温后过滤出白色粉末状固体，用乙酸乙酯多次清洗后烘干，得3-苄基苯并噻唑鎓溴。
将3.06g合成的3-苄基苯并噻唑鎓溴溶于10ml水，将2.87g双三甲烷磺酰亚胺锂加入其水溶液中，充分搅拌后静置至沉淀完全。过滤，取固体烘干，制得xii。
以xii作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.131g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率89％，产物由氯仿相凝胶渗透色谱测得相对数均分子量14700g/mol，分子量分布1.26。
实施例13：
将3.37g盐酸硫胺溶于5ml水，向其溶液中加入1.00g活化后的磺酸型离子交换树脂(安伯莱特离子交换树脂IR120)，充分搅拌12h后分离出树脂，烘干，制得固载型磺酸阴离子的噻唑鎓催化剂。以其作为催化剂，己内酯与催化剂质量比为10/1(己内酯2.85g、催化剂0.285g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率92％，产物由氯仿相凝胶渗透色谱测得相对数均分子量7400g/mol，分子量分布1.67。
实施例14：
以i作为催化剂，超干戊内酯与催化剂摩尔比为100/1(戊内酯2.50g、催化剂0.137g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚戊内酯，单体转化率76％，产物由氯仿相凝胶渗透色谱测得相对数均分子量100600g/mol，分子量分布1.05。
实施例15：
以i作为催化剂，对二氧环己酮与催化剂摩尔比为100/1(对二氧环己酮2.55g、催化剂0.137g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚对二氧环己酮，单体转化率65％，产物由氯仿相凝胶渗透色谱测得相对数均分子量7700g/mol，分子量分布1.52。
实施例16：
以i作为催化剂，对乙交酯与催化剂摩尔比为100/1(乙交酯2.90g、催化剂0.137g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚对二氧环己酮，单体转化率99％，产物由氯仿相凝胶渗透色谱测得相对数均分子量9700g/mol，分子量分布1.12。
实施例17：
以i作为催化剂，三亚甲基碳酸酯与催化剂摩尔比为100/1(三亚甲基碳酸酯2.55g、催化剂0.137g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率99％，产物由氯仿相凝胶渗透色谱测得相对数均分子量6900g/mol，分子量分布1.18。
实施例18：
以i作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.137g)投料后，封闭反应体系，油浴180℃中充分搅拌6h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率79％，产物由氯仿相凝胶渗透色谱测得相对数均分子量7300g/mol，分子量分布1.17。
实施例19：
以i作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.137g)投料后，封闭反应体系，油浴60℃中充分搅拌96h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率77％，产物由氯仿相凝胶渗透色谱测得相对数均分子量7200g/mol，分子量分布1.34。
实施例20：
以i作为催化剂，己内酯与催化剂摩尔比为10/1(己内酯2.85g、催化剂1.37g)投料后，封闭反应体系，油浴150℃中充分搅拌12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率99％，产物由氯仿相凝胶渗透色谱测得相对数均分子量9900g/mol，分子量分布1.16。
实施例21：
以i作为催化剂，己内酯与催化剂摩尔比为1000/1(己内酯2.85g、催化剂0.014g)投料后，封闭反应体系，油浴150℃中充分搅拌24h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率82％，产物由氯仿相凝胶渗透色谱测得相对数均分子量13300g/mol，分子量分布1.31。
实施例22：
以i作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.137g)投料，加入0.90g水后，封闭于水热反应釜，150℃下反应12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率99％，产物由氯仿相凝胶渗透色谱测得相对数均分子量1020g/mol，分子量分布2.00。
实施例23：
以i作为催化剂，己内酯与催化剂摩尔比为100/1(己内酯2.85g、催化剂0.137g)投料，加入0.027g苯甲醇后，封闭反应体系，150℃下反应12h后停止加热；将产物溶于20ml二氯甲烷，过滤后将滤液向80ml乙醇中滴加，滴加完后充分搅拌、静置至沉淀完全，将沉淀滤出、烘干得到聚己内酯，单体转化率96％，产物由氯仿相凝胶渗透色谱测得相对数均分子量8600g/mol，分子量分布1.20。
Claims (9)
1.一种以噻唑鎓盐为催化剂的环酯本体开环聚合方法，其特征在于：以噻唑鎓盐作为催化剂，以含羟基化合物作为引发剂，催化环酯本体开环聚合，得到聚酯，其中，所述的噻唑鎓盐的结构式为(Ⅰ):
其中，噻唑鎓部分的结构特征为：噻唑环上2-位碳上含氢，3-位氮上接R1基团，4、5-位碳上接R2、R3基团，其中R1、R2、R3选自任意基团；阴离子X为Tf2N-，PF6 -，BF4 -，R-SO3 -，R-COO-中的一种或几种。
2.如权利要求1所述的一种环酯本体开环聚合方法，其特征在于：所述的噻唑鎓部分为小分子噻唑鎓，或聚合的噻唑鎓，或被负载的噻唑鎓，或被复配的噻唑鎓。
3.如权利要求2所述的一种环酯本体开环聚合方法，其特征在于：所述的噻唑鎓为小分子噻唑鎓时，所述的噻唑鎓盐为结构式为(Ⅱ)、(Ⅲ)、(Ⅳ)、(Ⅴ)、(Ⅵ)；所述的噻唑鎓部分为聚合的、被负载的或者被复配的噻唑鎓时，所述的噻唑鎓盐结构式为(Ⅶ)，其中n表示聚合物聚合单元数，聚合单元数不限
4.如权利要求1或3所述的一种环酯本体开环聚合方法，其特征在于：所述的被催化的环酯结构式为环内酯(Ⅷ)、环交酯(Ⅸ)、环碳酸酯(Ⅹ)和环酯-醚(Ⅺ)中的一种或几种，其中R4、R6选自氢或具有1～5个碳原子的烷基，R5选自氢或甲基，R7选自氢或羟甲基，m1、m2表示重复单元数量为1～4
5.如权利要求1或3所述的一种环酯本体开环聚合方法，其特征在于：所述的环酯单体与所述的噻唑鎓盐催化剂的投料摩尔比为10-1000/1；所述方法的反应温度为60-180℃。
6.如权利要求3所述的一种环酯本体开环聚合方法，其特征在于：所述的环酯单体与所述的噻唑鎓盐催化剂的投料摩尔比为10-1000/1；所述方法的反应温度为60-180℃。
7.如权利要求5所述的一种环酯本体开环聚合方法，其特征在于：所述的开环聚合得到的聚酯分子量为1000-100000g/mol、分子量分布为1.05-2.00。
8.如权利要求6所述的一种环酯本体开环聚合方法，其特征在于：所述的开环聚合得到的聚酯分子量为1000-100000g/mol、分子量分布为1.05-2.00。
9.如权利要求2所述的一种环酯本体开环聚合方法，其特征在于：所述的噻唑鎓盐催化剂的制备方法为：
(1)由噻唑、4-取代噻唑、5-取代噻唑、4,5-二取代噻唑与卤代烃混合，在无溶剂或者以乙酸乙酯为溶剂下反应生成初始噻唑鎓盐；再对其中含有不饱和基团的初始噻唑鎓盐进行自由基聚合，可得到初始聚噻唑鎓盐；
(2)将步骤(1)中制备得到的所述初始噻唑鎓盐、初始聚噻唑鎓盐与含有阴离子X的盐在水或醇中，通过复分解反应或浓缩结晶实现阴离子部分的交换，得到所述的噻唑鎓盐催化剂。
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