CN115975159A - Squaramide ionic organic catalyst and synthesis method and application thereof - Google Patents
Squaramide ionic organic catalyst and synthesis method and application thereof Download PDFInfo
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- CN115975159A CN115975159A CN202211597660.3A CN202211597660A CN115975159A CN 115975159 A CN115975159 A CN 115975159A CN 202211597660 A CN202211597660 A CN 202211597660A CN 115975159 A CN115975159 A CN 115975159A
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- Prior art keywords
- isothiocyanate
- catalyst
- sec
- squaramide
- molecular weight
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- WUACDRFRFTWMHE-UHFFFAOYSA-N 3,4-diaminocyclobut-3-ene-1,2-dione Chemical compound NC1=C(N)C(=O)C1=O WUACDRFRFTWMHE-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000001308 synthesis method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 54
- 238000012648 alternating copolymerization Methods 0.000 claims abstract description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 66
- -1 cyclic ester Chemical class 0.000 claims description 39
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 claims description 38
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 35
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 33
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 229940117953 phenylisothiocyanate Drugs 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 16
- VHBFEIBMZHEWSX-UHFFFAOYSA-N 2-isothiocyanatopropane Chemical compound CC(C)N=C=S VHBFEIBMZHEWSX-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 12
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- NSDDRJXKROCWRZ-UHFFFAOYSA-N 1-isothiocyanato-2-methylpropane Chemical compound CC(C)CN=C=S NSDDRJXKROCWRZ-UHFFFAOYSA-N 0.000 claims description 7
- TUFJIDJGIQOYFY-UHFFFAOYSA-N 2-isothiocyanatobutane Chemical compound CCC(C)N=C=S TUFJIDJGIQOYFY-UHFFFAOYSA-N 0.000 claims description 7
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 claims description 7
- MDKCFLQDBWCQCV-UHFFFAOYSA-N benzyl isothiocyanate Chemical compound S=C=NCC1=CC=CC=C1 MDKCFLQDBWCQCV-UHFFFAOYSA-N 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- ZUWFBQUHBOUPFK-UHFFFAOYSA-N 1-chloro-2-isothiocyanatoethane Chemical compound ClCCN=C=S ZUWFBQUHBOUPFK-UHFFFAOYSA-N 0.000 claims description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 claims description 4
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical group O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 4
- 239000001439 (2R)-2-isothiocyanatobutane Substances 0.000 claims description 3
- CCEFMUBVSUDRLG-KXUCPTDWSA-N (4R)-limonene 1,2-epoxide Natural products C1[C@H](C(=C)C)CC[C@@]2(C)O[C@H]21 CCEFMUBVSUDRLG-KXUCPTDWSA-N 0.000 claims description 3
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 claims description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- SYFZCLMMUNCHNH-UHFFFAOYSA-N 2-(prop-2-ynoxymethyl)oxirane Chemical compound C#CCOCC1CO1 SYFZCLMMUNCHNH-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 claims description 3
- QAADZYUXQLUXFX-UHFFFAOYSA-N N-phenylmethylthioformamide Natural products S=CNCC1=CC=CC=C1 QAADZYUXQLUXFX-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000005192 alkyl ethylene group Chemical group 0.000 claims description 3
- 235000016720 allyl isothiocyanate Nutrition 0.000 claims description 3
- CPEKAXYCDKETEN-UHFFFAOYSA-N benzoyl isothiocyanate Chemical compound S=C=NC(=O)C1=CC=CC=C1 CPEKAXYCDKETEN-UHFFFAOYSA-N 0.000 claims description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- RYBJNWIQNLZNPE-UHFFFAOYSA-N isothiocyanatomethylcyclohexane Chemical compound S=C=NCC1CCCCC1 RYBJNWIQNLZNPE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 79
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 72
- 239000012043 crude product Substances 0.000 description 62
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 29
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- 238000007334 copolymerization reaction Methods 0.000 description 15
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- 229910052739 hydrogen Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- GHBSPIPJMLAMEP-UHFFFAOYSA-N 6-pentyloxan-2-one Chemical compound CCCCCC1CCCC(=O)O1 GHBSPIPJMLAMEP-UHFFFAOYSA-N 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Chemical group 0.000 description 9
- PBLNHHSDYFYZNC-UHFFFAOYSA-N (1-naphthyl)methanol Chemical compound C1=CC=C2C(CO)=CC=CC2=C1 PBLNHHSDYFYZNC-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000012264 purified product Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 150000007530 organic bases Chemical class 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- HBNYJWAFDZLWRS-UHFFFAOYSA-N ethyl isothiocyanate Chemical compound CCN=C=S HBNYJWAFDZLWRS-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 150000002540 isothiocyanates Chemical class 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
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- 239000004632 polycaprolactone Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920001432 poly(L-lactide) Polymers 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- TXOFSCODFRHERQ-UHFFFAOYSA-N N,N-Dimethylphenethylamine Chemical compound CN(C)CCC1=CC=CC=C1 TXOFSCODFRHERQ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
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- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PZUDSCYHVMUKLX-UHFFFAOYSA-M [NH4+].[OH-].[OH-].C[N+](C)(C)CC1=CC=CC=C1 Chemical compound [NH4+].[OH-].[OH-].C[N+](C)(C)CC1=CC=CC=C1 PZUDSCYHVMUKLX-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
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- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LBUSGXDHOHEPQQ-UHFFFAOYSA-N propane-1,1,1-triol Chemical compound CCC(O)(O)O LBUSGXDHOHEPQQ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Images
Abstract
The invention belongs to the technical field of catalysts and application, and relates to a squaramide ionic organic catalyst, a synthesis method and application thereof, wherein the structural formula of the squaramide ionic organic catalyst is shown as the following formula:
the catalyst disclosed by the invention has the advantages of simple structure, easy operation of a synthetic route, low cost, good catalytic activity in ring-opening polymerization reaction and alternating copolymerization reaction, capability of improving the purity and yield of a polymer, and stronger industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts and application, and relates to a squaramide ionic organic catalyst, a synthesis method and application thereof.
Background
Compared with organic metal catalysts, the organic/metal-free catalyst has the advantages of low biotoxicity, stable structure, good solubility, easy purification, good water-oxygen tolerance, easy obtainment of raw materials, simple and convenient synthesis, environmental protection and the like, so that an organic/metal-free catalytic system obtains excellent achievement in the aspects of regulating and controlling a microscopic chain structure, a three-dimensional structure, a sequence structure, a topological structure and the like of a polymer.
The organic/metal-free catalyst mainly comprises organic bases, organic (proton or Lewis) acids and hydrogen bond donor-acceptor bifunctional catalysts. The organic base catalyst is widely used, mainly comprises neutral (uncharged) organic bases such as N-heterocyclic carbenes, amidines, guanidines, phosphazene bases and organophosphorus compounds, and can activate substrates (such as an initiator), monomers and the like by exerting the alkalinity or nucleophilicity of the neutral (uncharged) organic bases. In a polymerization reaction system, the catalytic activity of an organic base catalyst is usually dependent on the alkalinity, but for a neutral organic base, the stronger alkalinity is usually required to have a more complex conjugated structure, and the complex conjugated structure can cause the limitation of the range and the flexibility of the activity adjustment of the catalyst, the complexity of the catalyst synthesis process, the increase of the cost and the reduction of the practicability, and the limitations of the neutral organic base greatly limit the industrial application of the catalyst.
The literature Zhuolun Jiang, et al, ionic organic catalysts with a Urea Anion and Tetra-N-butyl Ammonium Cation for Rapid, selective, and Versatile Ring-Opening Polymerization of latex. ACS Macro Lett.2019,8 (7), 759-765, through a simple dehydration reaction between Tetra-N-butylammonium hydroxide and N, N-disubstituted thiourea/Urea, a series of hydrogen bond donor acceptor bifunctional Ionic organic catalysts are obtained, and have remarkable high efficiency and controllability for the catalysis of the Ring-Opening Polymerization of lactide. After thiourea/urea and quaternary ammonium base are ionized through dehydration reaction, the anion part activates an initiator and hydroxyl at the tail end of a growing chain through hydrogen bond action, which is a main source of catalytic activity; and the residual NH group can activate the monomer through the action of hydrogen bond, thereby realizing double and synergistic activation of the monomer and the initiator and simultaneously improving the catalytic efficiency and selectivity. Compared with neutral organic alkali, the ionic organic catalyst has simpler structure and preparation method, and the catalytic activity can be widely and flexibly adjusted through the abundant substituent group structures on two N atoms. However, the full play of the bifunctional concerted catalysis requires that the residual NH group after ionization still has a strong hydrogen bond donor function, which requires that the catalyst precursor has sufficient acidity, but the intrinsic acidity of urea is low, so that a benzene ring connected with a plurality of strong electron-withdrawing groups (such as F atoms, trifluoromethyl and the like) is often required to be used as an N-substituent; although the intrinsic acidity of thiourea is higher than that of urea, a benzene ring with a certain amount of electron-withdrawing groups (such as Cl, F atoms, trifluoromethyl and the like) is required to be an N-substituent to have sufficient hydrogen bond donor effect, and the sulfur atom causes the biotoxicity of the catalyst to be non-negligible. Research shows that benzene ring substituent with electron-withdrawing conjugation effect (such as nitro, cyano, carbonyl and the like) can improve the acidity of thiourea and urea, but is also a strong hydrogen bond acceptor to cause the damage or complete loss of catalytic activity, thereby reducing the yield and purity of products in polymerization reaction.
Disclosure of Invention
The invention discloses a squaramide ionic organic catalyst, a synthesis method and application thereof, aiming at the technical problems of low activity, complex structure and high cost of the existing ionic organic catalyst.
In order to achieve the purpose, the invention adopts the technical scheme that:
a squaramide ionic organic catalyst has a structural formula shown as the following formula:
in the formula (I);
y represents N or P;
R 3 ，R 4 ，R 5 ，R 6 each represents four independent hydrocarbon groups having 1 to 12 carbon atoms;
R 1 and R 2 Each independently selected from C1-C10 linear alkyl, cyclohexyl, tertiary butyl, isopropyl, allyl, phenyl, naphthyl and R 7 -phenyl or R 7 -a naphthyl group; the R is 7 is-F, -Cl, -Br, -CF 3 、-OCH 3 And at least one substituent of alkyl and N, N-disubstituted alkyl.
A method for synthesizing a squaramide ionic organic catalyst comprises the following steps:
uniformly mixing the compound A, the compound B and an organic solvent tetrahydrofuran, reacting for 2-4 h under the vacuum condition of the pressure of 0.01-1 mbar, and then performing dehydration reaction at 70-80 ℃ to obtain a solid product, namely the squaramide ionic organic catalyst;
the structural formula of the compound A is shown as the formula (1):
in the above formula, R 1 And R 2 Each independently selected from C1-C10 straight-chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl and R 7 -phenyl or R 7 -a naphthyl group; said R is 7 is-F, -Cl, -Br, -CF 3 、-OCH 3 At least one substituent of alkyl and N, N-disubstituted alkyl;
the structural formula of the compound B is shown as the formula (2):
in the above formula, Y represents N or P; r 3 ，R 4 ，R 5 ，R 6 Each represents four independent hydrocarbon groups having 1 to 12 carbon atoms.
Further, the molar ratio of the compound A to the compound B is (1-10): 1, and the dosage ratio of the compound B to the organic solvent is 0.5mmol:15ml; the organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, toluene or acetonitrile.
An application of squaramide ionic organic catalyst in ring-opening polymerization reaction of cyclic ester monomer or cyclic carbonate monomer.
An application of squaramide ionic organic catalyst in the alternative copolymerization reaction of epoxy compound and isorhodanic ester compound.
An application of squaramide ionic organic catalyst in the alternative copolymerization reaction of epoxy compound and phthalic anhydride is disclosed.
Further, the reaction conditions in the application are as follows: the temperature is 20-60 ℃, and the time is 5 min-68 h.
Further, the cyclic ester monomer is epsilon-caprolactone, delta-valerolactone, racemic lactide, levorotatory lactide, dextrorotatory lactide or delta-alkyl valerolactone of C1-C12; the cyclic carbonate monomer is trimethylene carbonate.
Further, the epoxy compound is ethylene oxide, C1-C20 linear alkyl ethylene oxide, C1-C16 linear alkyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, glycidyl methacrylate, cyclohexene oxide, 4-vinyl cyclohexene oxide or limonene oxide.
Further, the isothiocyanate compound is at least one of methyl isothiocyanate, linear alkyl isothiocyanate, alicyclic isothiocyanate, isopropyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, benzyl isothiocyanate, phenyl isothiocyanate, o/m/p-toluene isothiocyanate, benzoyl isothiocyanate, chloroethyl isothiocyanate, cyclohexylmethyl isothiocyanate and allyl isothiocyanate; the carbon atom number of the straight-chain alkyl is 2-20, and the carbon atom number of the alicyclic ring in the alicyclic isothiocyanate is 3-12.
The invention has the beneficial effects that:
1. compared with the common classical hydrogen bond donor organic micromolecules, the squaramide derivative used as the raw material of the catalyst has higher acidity when containing the same N-substituent, can avoid introducing S and halogen (mainly Cl and F) atoms in the molecular structure of the catalyst, and can obtain sufficient hydrogen bond strength and synergistic catalytic action only by constructing the catalyst through the C, H, O, N atom of the squaramide, thereby simplifying the structure and the synthesis path of the catalyst, reducing the cost and further improving the biological safety and the environmental friendliness of the organic catalyst.
2. In the invention, the squaramide derivative and tetraalkyl substituted ammonium hydroxide/phosphorus are subjected to dehydration reaction, and due to the structure of the squaramide, a squaramide ionic organic catalytic system with rich structure and stable property can be easily synthesized,
3. in the invention, the squaramide ionic organic catalyst can flexibly change the structures of two N-substituent groups and tetraalkylammonium/phosphorus counter ions and the proportion of the ionic part and the neutral part of the catalyst to adjust the catalytic activity so as to adapt to the requirements of different polymerization reactions. In addition, the squaramide ionic organic catalyst can realize double activation of the monomer and the initiator under the action of anions and reserved NH groups, and the polymerization reaction is ensured to be carried out controllably and efficiently to a great extent, so that the problems of limited activity regulation range and flexibility of the existing single-component organic strong base type catalyst are solved.
4. In the invention, the squaramide ionic organic catalyst is matched with different initiators (such as functionalized initiators, multifunctional initiators and macroinitiators) and monomers for use, ring-opening polymerization of cyclic ester monomers and cyclic carbonate monomers is efficiently and controllably carried out, and polymers (with structural characteristics of end group functionalization, side group functionalization, block, multiblock, star, grafting and the like) with controllable molecular weight and definite and rich structures are prepared, particularly copolymers taking polyester/polycarbonate and polyester/polycarbonate as main components, and the application is flexible and convenient.
5. In the invention, the squaramide ionic organic catalyst can effectively inhibit or even eliminate side reactions such as trimerization of isothiocyanate, dimerization of epoxy and isothiocyanate and the like in the alternating copolymerization of epoxy compound and isothiocyanate, improve the purity and yield of copolymer, lead the epoxy and isothiocyanate compound to carry out strict alternating copolymerization reaction, and completely avoid the homopolymerization of epoxy and the generation of polyether chain segment.
6. In the invention, the squaramide ionic organic catalyst can realize the alternating copolymerization of the epoxy compound and the phthalic anhydride at a lower temperature (such as room temperature), so that the reaction is free from the requirements on high temperature and high pressure conditions, and the simplicity, flexibility and safety of operation are greatly improved.
Drawings
FIG. 1 is a SEC curve of a crude product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A 3;
FIG. 2 shows the crude product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3 1 HNMR spectrogram;
FIG. 3 is a SEC curve of a crude product obtained by Sq5A3 catalyzing the ring-opening polymerization of delta-valerolactone;
FIG. 4 shows the crude product obtained by Sq5A3 catalyzing the ring-opening polymerization of delta-valerolactone 1 HNMR spectrogram;
FIG. 5 is a SEC curve of a crude product obtained by catalyzing ring-opening polymerization of epsilon-caprolactone by Sq5A 2;
FIG. 6 shows the crude product obtained by Sq5A2 catalyzing the ring-opening polymerization of epsilon-caprolactone 1 H NMR spectrum;
FIG. 7 is a SEC curve of the purified product obtained from the ring-opening polymerization of lactide catalyzed by Sq1A 3;
FIG. 8 shows the purified product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3 1 HNMR spectrogram;
FIG. 9 is a MALDI-TOF spectrum of a purified product obtained by catalyzing lactide ring-opening polymerization with Sq1A 3;
FIG. 10 is a SEC curve of a purified product obtained by alternate copolymerization of Sq5A3 catalytic propylene oxide and phenyl isothiocyanate;
FIG. 11 shows the purified product obtained by alternate copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by Sq5A3 1 HNMR spectrogram;
FIG. 12 is a SEC curve of a crude product obtained by alternate copolymerization of propylene oxide and isopropyl isothiosulfate catalyzed by Sq5A 3;
FIG. 13 shows the crude product obtained by Sq5A3 catalyzed alternating copolymerization of propylene oxide and isopropyl isothiosulfate 1 HNMR spectrogram;
FIG. 14 is a SEC curve of a crude product obtained by alternate copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq5A 3;
FIG. 15 shows the crude product obtained by Sq5A3 catalyzing the alternating copolymerization of propylene oxide and phthalic anhydride 1 HNMR spectrogram;
FIG. 16 is a SEC curve of a crude product obtained by alternate copolymerization of Sq10A3 catalyzed by propylene oxide and phthalic anhydride;
FIG. 17 shows the crude product obtained by alternate copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq10A3 1 HNMR spectrogram
FIG. 18 is a SEC curve of a crude product obtained by alternate copolymerization of Sq5A3 catalytic styrene oxide and phthalic anhydride;
FIG. 19 shows the catalytic oxidation of styrene with Sq5A3Crude product obtained by alternating copolymerization of phthalic anhydride 1 HNMR spectrogram.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The invention prepares the squaramide and quaternary ammonium/phosphorus alkali into the ionic organic catalyst through dehydration reaction, and then applies the ionic organic catalyst to ring-opening polymerization reaction of cyclic ester or cyclic carbonate monomer, alternating copolymerization of epoxy compound and phthalic anhydride, and alternating copolymerization of epoxy compound and isothiocyanate.
The formula of the squaramide ionic organic catalyst provided by the invention is shown as the following formula:
in the formula (I);
y represents N or P;
R 3 ，R 4 ，R 5 ，R 6 each represents four independent hydrocarbon groups having 1 to 12 carbon atoms;
R 1 and R 2 Each independently selected from C1-C10 linear alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl and R 7 -phenyl or R 7 -a naphthyl group; r 7 is-F, -Cl, -Br, -CF 3 、-OCH 3 And at least one substituent of alkyl and N, N-disubstituted alkyl.
The synthesis method of the squaramide ionic organic catalyst comprises the following steps:
uniformly mixing the compound A, the compound B and an organic solvent tetrahydrofuran, reacting for 2-4 h under the vacuum condition of the pressure of 0.01-1 mbar, and then performing dehydration reaction at 70-80 ℃ to obtain a solid product, namely the squaramide ionic organic catalyst;
the structural formula of the compound A is shown as a formula (1).
In the above formula, R 1 And R 2 Each independently selected from C1-C10 linear alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl or containing-F, -Cl, -Br and-CF 3 、-OCH 3 Phenyl and naphthyl with at least one substituent of alkyl, N-disubstituted alkyl.
The structural formula of the compound B is shown as a formula (2).
In the above formula, Y represents N or P; r 3 ，R 4 ，R 5 ，R 6 Each represents four independent hydrocarbon groups having 1 to 12 carbon atoms.
The organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, toluene or acetonitrile. Preferably, the organic solvent is tetrahydrofuran.
In the invention, the molar ratio of the compound A to the compound B is (1-10): 1, and the dosage ratio of the compound B to the organic solvent is 0.05mmol:15ml of the solution.
The reaction formula of the synthesis method is shown below.
The squaramide ionic organic catalyst prepared by the invention has good catalytic activity, simple synthesis route, simple catalyst structure, low cost and good catalytic activity, and can be well used for the ring-opening polymerization reaction and the alternating copolymerization reaction of monomers.
Preferably, the squaramide ionic organic catalyst is used for ring-opening polymerization of cyclic ester monomers or cyclic carbonate monomers.
More preferably, the cyclic ester monomer is epsilon-caprolactone (. Epsilon. -CL), delta-valerolactone (. Delta. -VL), racemic Lactide (LA), levolactide (LLA), dextrolactide (DLA), or delta-alkyl valerolactone (5-alkyl-VL) having an alkyl group with 1 to 12 carbon atoms. The cyclic carbonate monomer is trimethylene carbonate (TMC). The specific structural formula is as follows.
Preferably, the squaramide ionic organic catalyst is used for alternating copolymerization of an epoxy compound and an isothiocyanate compound and alternating copolymerization of the epoxy compound and phthalic anhydride.
Preferably, the epoxy compound is at least one of (1) ethylene oxide, (2) C1 to C20 linear alkyl ethylene oxide, (3) styrene oxide, (4) cyclohexene oxide, (5) 4-vinylcyclohexane oxide, (6) limonene oxide, (7) C1 to C16 linear alkyl glycidyl ether, (8) isopropyl glycidyl ether, (9) tert-butyl glycidyl ether, (10) 2-ethylhexyl glycidyl ether, (11) phenyl glycidyl ether, (12) benzyl glycidyl ether, (13) allyl glycidyl ether, (14) propargyl glycidyl ether, and (15) glycidyl methacrylate. The structure is shown in the following figure.
Preferably, the isothiocyanate compound is: methyl isothiocyanate, (2) linear alkyl isothiocyanate, wherein the linear alkyl group contains 2-20 carbon atoms, (3) alicyclic isothiocyanate, wherein the alicyclic group contains 3-12 carbon atoms, (4) isopropyl isothiocyanate, (5) sec-butyl isothiocyanate, (6) isobutyl isothiocyanate, (7) benzyl isothiocyanate, (8) phenyl isothiocyanate, (9) o/m/p-toluene isothiocyanate, (10) benzoyl isothiocyanate, (11) chloroethyl isothiocyanate, (12) cyclohexylmethyl isothiocyanate and (13) allyl isothiocyanate. The specific structural formula is as follows.
Further, the polymerization reaction adopts solution polymerization or bulk polymerization, i.e. the catalyst directly participates in the polymerization reaction, or the catalyst is prepared into solution to participate in the reaction.
The solvent used in the solution polymerization is one or a mixture of more than two of toluene, acetone, tetrahydrofuran, 1,4-dioxane, dichloromethane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, gamma-butyrolactone, propylene carbonate and acetonitrile. The concentration of the catalyst in the solution is 0.04 mol/L-0.2 mol/L.
Further, according to the polymerization reaction, an alcohol initiator can be optionally added according to the reaction requirement, and the molar ratio of the ionic organic catalyst to the alcohol initiator is (0.01-10): 1.
Preferably, the alcoholic initiator is: methanol or a linear alkyl alcohol having 2 to 18 carbon atoms, (2) isopropanol, (3) 2-butanol, (4) t-butanol, (5) a 1-phenyl linear alkyl alcohol having 1 to 10 alkyl carbon atoms, (6) allyl alcohol or a linear terminal alkenyl 1-alcohol having 2 to 10 saturated carbon atoms, (7) 1-naphthalenemethanol, (8) maleic glycol, (9) ethylene glycol, (10) 1,4-butanediol, (11) terephthalyl alcohol, (12) 1,1,1-trimethylolpropane, (13) glycerol, (14) pentaerythritol, (15) dipentaerythritol, (16) sorbitol, (17) tripentaerythritol, (18) polyethylene glycol or polyethylene glycol monomethyl ether having a number average molecular weight of 400 to 20000 g/mol. The specific structural formula is as follows.
Furthermore, the reaction condition of the catalyst is that the temperature is 20-60 ℃ and the reaction time is 5 min-68 h.
The catalyst, synthesis method and application in ring-opening polymerization and alternating copolymerization provided by the present invention are described in several groups of specific embodiments.
In the following examples, the conversion of cyclic ester monomer or cyclic carbonate monomerAnd structural features of the polymer were tested by Bruker AV600 NMR spectrometer, CDCl 3 、DMSO-d 6 As solvent, tetramethylsilane as internal standard.
The molecular weight and molecular weight dispersity of the polyester or polycarbonate are measured by volume exclusion chromatography (SEC), the instrument adopts a volume exclusion chromatograph of 1260 Infinity model of Agilent (America), the mobile phase is tetrahydrofuran, the column temperature is 35 ℃, and the flow rate is 1mL/min; calibration curves were prepared with a series of polystyrene standards.
The mass peak of the polyester was tested using a Bruker Autoflex III Smartbeam MADLDL-TOF mass spectrometer. The sample was dissolved in THF to prepare a 10mg/mL solution, which was then mixed with a 10mg/mL THF solution of sodium trifluoroacetate at a volume ratio of 5/1. The mixed solution was mixed with a solution of 2,5-dihydroxybenzoic acid in THF (20 mg/mL) at a volume ratio of 1/10, 0.4. Mu.L of the mixed solution was dropped on the test plate for testing, and the mass spectrum peak of the sample was obtained by the cation reflection mode.
The parts stated in the examples below are in molar parts.
Otherwise not specifically described is a routine practice in the art.
Example 1
This example is the synthesis of 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq 1A 3).
The synthesis method of the catalyst Sq1A3 comprises the following steps:
1,4-diphenylsquaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were added to a 50mL Schlenk flask and stirred at 40 ℃ for 4h. Tetrahydrofuran (THF) is then slowly pumped off under a vacuum of 0.1 to 0.01mbar and the remaining solid is heated to 80 ℃ under vacuum for 2h. The resulting solid was dissolved in 2.7mL of dimethyl sulfoxide (DMSO) to prepare a 0.2mol/L catalyst solution.
Example 2
This example is the synthesis of 1,4-bis (4-p-methoxyphenyl) squaramide tetrabutylammonium catalyst (Sq 2A 3).
The synthesis method of the catalyst Sq2A3 comprises the following steps:
1,4-bis (4-p-methoxyphenyl) squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) was mixed well with 15mL Tetrahydrofuran (THF). The other operations were the same as the synthesis in example 1.
Example 3
This example is the synthesis of 1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3).
The synthesis method of the catalyst Sq5A3 comprises the following steps:
1,4-dicyclohexyl squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well. The other operations were the same as the synthesis in example 1.
Example 4
This example is a synthesis of 1,4-dicyclohexyl squaramide tetrabutylphosphonium catalyst (Sq 5P 1).
The synthesis method of the catalyst Sq5P1 comprises the following steps:
1,4-dicyclohexyl squaramide (0.648 mmol), tetrabutyl phosphonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well, and the other operations were the same as those in the synthesis of example 1.
Example 5
This example is a synthesis of 1,4-dicyclohexyl squaramide tetramethylamine catalyst (Sq 5A 1).
The synthesis method of the catalyst Sq5A1 comprises the following steps:
1,4-dicyclohexyl squaramide (0.648 mmol), tetramethylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well and the other operations were the same as in example 1.
Example 6
This example is a synthesis of 1,4-dicyclohexyl squaramide benzyl trimethylamine catalyst (Sq 5A 2).
The synthesis method of the catalyst Sq5A2 comprises the following steps:
1,4-dicyclohexyl squaramide (0.648 mmol), benzyltrimethylammonium ammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well and otherwise the same procedure as in example 1 was followed.
Example 7
This example is a synthesis of 1,4- (2,5-di-p-methoxyphenyl) squaramide tetrabutyl ammonium catalyst (Sq 3A 3).
The synthesis method of the catalyst Sq3A3 comprises the following steps:
1,4- (2,5-di-p-methoxyphenyl) squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well and the other operations were the same as in the synthesis of example 1.
Example 8
This example is a synthesis of 1,4- (3,4,5-tri-p-methoxyphenyl) squaramide tetrabutyl ammonium catalyst (Sq 4A 3).
The synthesis method of the catalyst Sq4A3 comprises the following steps:
1,4- (3,4,5-tris-p-methoxyphenyl) squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well and otherwise the procedure was the same as in the synthesis of example 1.
Example 9
This example is the synthesis of 1,4-di-tert-butyl squaramide tetrabutylammonium catalyst (Sq 10A 3).
The synthesis method of the catalyst Sq10A3 comprises the following steps:
1,4-tert-butyl squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well and the other operations were the same as in the synthesis of example 1.
Example 10
This example is the synthesis of 1,4-tricyclo [3,3,1,1 (3,7) ] decylbenzamide tetrabutylammonium catalyst (Sq 11A 3).
The synthesis method of the catalyst Sq11A3 comprises the following steps:
1,4-tricyclo [3,3,1,1 (3,7) ] decyl squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15mL Tetrahydrofuran (THF) were mixed well and otherwise the procedure was the same as that of example 1.
Examples 1 to 10 above list 10 groups of squaramide ionic organic catalysts with different structures, but the structure of the squaramide ionic organic catalyst provided by the present invention is not limited thereto; in addition, in the synthesis process, the dosage ratio of the compounds and the synthesis parameters are arbitrarily selected within the range of the invention, and the squaramide ionic organic catalyst can be obtained.
The catalytic activity of the catalyst will be further elucidated by the use of the catalysts of examples 1 to 10.
Example 11
This example is the ring opening polymerization of Lactide (LA) catalyzed by 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq 1A 3).
In this example, the reaction formula of the ring-opening polymerization is as follows.
The method for preparing Polylactide (PLA) by catalyzing the ring-opening polymerization of Lactide (LA) by the catalyst (Sq 1A 3) is as follows.
(1) 2.88gLA was dissolved in 26.5mL of Dichloromethane (DCM) to make a 0.75mol/L LA solution, and 0.3160g of 1-naphthalenemethanol (NtA) was dissolved in 40mL of DCM to make a 0.05mol/L NtA solution.
(2) 75 parts of LA (1.0 mL, 0.75mmol) and 1 part of NtA (200. Mu.L, 0.01 mmol) and 1 part of Sq1A3 (50. Mu.L, 0.01 mmol) as a catalyst were added to a dried container under an inert gas atmosphere, and after 5 minutes of reaction at room temperature, 0.5mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was subjected to SEC and SEC 1 HNMR tests, the remaining crude product was poured into 20mL of methanol to precipitate the polymer, and the final product was collected and dried in a vacuum oven at 40 ℃ overnight.
In this example, the SEC curve of the crude product prepared by the ring-opening polymerization of lactide catalyzed by catalyst Sq1A3 and 1 HNMR spectra, as shown in FIGS. 1 and 2.
See FIGS. 1 and 2, SEC and 1 as a result of H NMR, the conversion of lactide LA was 90%, and the theoretical number average molecular weight (M) was calculated n,th ) 9.7kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 15.3kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 9.9kg/mol, molecular weight distribution
Is 1.10.
Example 12
This example is a1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq 1A 3) catalyzed ring opening polymerization of gamma-Butyrolactone (BL).
Catalyst Sq1A3 was dissolved in 2.7mL of γ -Butyrolactone (BL), and the other operation steps were the same as in example 11. After 5min reaction at room temperature, 0.5mL of acetic acid was added to stop the reaction, and a small amount of the crude product was taken for SEC and SEC 1 And H NMR test.
The conversion of BL is 81%, the theoretical number average molecular weight (M) is calculated n,th ) 8.7kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 12.3kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 8.7kg/mol, molecular weight distribution 1.07.
Example 13
This example is 1,4-bis (4-p-methoxyphenyl) squaramide tetrabutylammonium catalyst (Sq 2A 3) catalyzed LA ring opening polymerization.
The method for preparing poly PLA by the ring-opening polymerization of LA catalyzed by the catalyst (Sq 2A 3) is the same as that of example 11.
According to SEC and 1 as a result of H NMR, the conversion of LA was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 10.8kg/mol, number average molecular weight (M) by SEC n,SEC ) The content of the reaction mixture was 14.3kg/mol, 1 number average molecular weight (M) calculated by HNMR n,NMR ) 10.1kg/mol, molecular weight distribution
Is 1.15.
Example 14
This example is 1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) catalyzed LA ring opening polymerization.
The method for preparing PLA by catalyzing LA ring-opening polymerization with the catalyst (Sq 5A 3) is the same as that of example 11.
According to SEC and 1 as a result of H NMR, the conversion of LA was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 10.8kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 10.8kg/mol of a polymer, 1 the number average molecular weight calculated by HNMR is (M) n,NMR ) 11.5kg/mol, molecular weight distribution
Was 1.75.
Example 15
This example is a1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) catalyzed delta-valerolactone (delta-VL) ring opening polymerization.
In this example, the reaction formula for ring-opening polymerization of δ -valerolactone (δ -VL) is shown below.
100 parts of delta-VL (0.9mL, 9mmol) and 1 part of benzyl alcohol (90. Mu.L, 0.09 mmol) and 1 part of Sq5A3 catalyst (0.45mL, 0.09mmol) were added to a dried container under an inert gas atmosphere, the reaction was terminated by adding 0.5mL of acetic acid after 5min at room temperature, and a small amount of the crude product was subjected to SEC and SEC 1 And H NMR test. The remaining crude product was poured into 20mL of methanol to precipitate the polymer. The final product was collected and dried in a vacuum oven at 40 ℃ overnight.
SEC curve of crude product prepared by catalyzing ring-opening polymerization of delta-valerolactone by catalyst Sq5A3 and 1 the H NMR spectrum is shown in FIGS. 3 and 4.
See FIGS. 3 and 4, in accordance with SEC and 1 as a result of H NMR, the conversion of. Delta. -VL was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 10.0kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 12.4kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 10.1kg/mol, molecular weight distribution
Is 1.36.
Example 16
This example is a1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) catalyzed ring opening polymerization of epsilon-caprolactone (. Epsilon. -CL).
In this example, the ring-opening polymerization formula of ε -caprolactone (. Epsilon. -CL) is as follows.
100 parts of ε -CL (1.0 mL,9 mmol), 1 part of benzyl alcohol (90. Mu.L, 0.09 mmol) and 1 part of Sq5A3 catalyst (0.45mL, 0.09mmol) were added to a dried container under an inert gas atmosphere, and after 2 hours at room temperature, 0.5mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was subjected to SEC and SEC 1 H NMR measurement. The remaining crude product was poured into 20mL of methanol to precipitate the polymer, and the final product was collected and dried in a vacuum oven at 40 ℃ overnight.
In the present example, according to SEC and 1 as a result of H NMR, the conversion of ε -CL was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 11.4kg/mol, number average molecular weight (M) by SEC n,SEC ) The content of the reaction mixture was 14.6kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 11.9kg/mol, molecular weight distribution
Is 1.29.
Example 17
This example is a1,4-dicyclohexyl squaramide tetrabutylphosphonium catalyst (Sq 5P 1) catalyzed ring opening polymerization of ε -CL.
The method for preparing Polycaprolactone (PCL) by catalyzing ring-opening polymerization of epsilon-caprolactone (epsilon-CL) by using catalyst (Sq 5P 1) is the same as that in example 16, after the reaction is carried out for 2 hours at room temperature, 0.5mL of acetic acid is added to terminate the reaction, and a small amount of crude product is taken to carry out SEC and SEC 1 And H NMR test.
According to SEC and 1 as a result of H NMR, the conversion of ε -CL was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 11.4kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 13.4kg/mol, 1 number average molecular weight (M) calculated by HNMR n,NMR ) 11.9kg/mol, molecular weight distribution
Is 1.21.
Example 18
This example is a1,4-dicyclohexyl squaramide tetramethylamine catalyst (Sq 5A 1) catalyzed ring opening polymerization of ε -CL.
The method for preparing PCL by catalyzing ring-opening polymerization of epsilon-CL with the catalyst (Sq 5A 1) is the same as that of example 16. After 2h of reaction at room temperature, 0.5mL of acetic acid was added to stop the reaction, and a small amount of the crude product was taken for SEC and 1 h NMR measurement.
According to SEC and 1 h NMR results according to SEC and 1 as a result of H NMR, the conversion of ε -CL was 76%, and the theoretical number average molecular weight (M) was calculated n,th ) 8.7kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 11.2kg/mol of a catalyst, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 8.9kg/mol, molecular weight distribution
It was 1.07.
Example 19
This example is a1,4-dicyclohexyl squaramide benzyltrimethylamine catalyst (Sq 5A 2) catalyzed ring opening polymerization of ε -CL.
The method for preparing PCL by catalyzing ring-opening polymerization of epsilon-CL with the catalyst (Sq 5A 2) is the same as that in example 16, after reacting for 2 hours at room temperature, 0.5mL of acetic acid is added to terminate the reaction, and a small amount of crude product is taken to carry out SEC and SEC 1 H NMR measurement.
SEC curve of crude product prepared by catalyzing ring-opening polymerization of epsilon-caprolactone by Sq5A2 catalyst and 1 the H NMR spectra are shown in FIGS. 5 and 6, respectively.
See fig. 5 and 6, in terms of SEC and 1 as a result of HNMR, the conversion of ε -CL was 45%, and the theoretical number average molecular weight (M) was calculated n,th ) 5.2kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 6.7kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 5.4kg/mol, molecular weight distribution
Is 1.15.
Example 20
This example is a1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) catalyzed delta-decalactone (delta-DL) ring opening polymerization.
The reaction formula for the ring-opening polymerization of delta-decalactone (delta-DL) in this example is as follows.
100 parts of delta-DL (1.6 mL,9 mmol), 1 part of benzyl alcohol (90. Mu.L, 0.09 mmol) and 1 part of Sq5A3 catalyst (0.45mL, 0.09mmol) were put into a dried vessel under an inert gas atmosphere, reacted at room temperature for 15min, then 0.5mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was subjected to SEC and SEC 1 HNMR test. The remaining crude product was poured into 20mL of methanol to precipitate the polymer, and the final product was collected and dried in a vacuum oven at 40 ℃ overnight.
According to SEC and 1 as a result of HNMR, the conversion of. Delta. -DL was 89%, and the theoretical number average molecular weight (M) was calculated n,th ) 15.2kg/mol, number average molecular weight (M) by SEC n,SEC ) The weight ratio of the total weight of the polymer is 19.7kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 15.6kg/mol, molecular weight distribution
Was 1.17.
Example 21
This example is the ring-opening polymerization of L-lactide (LLA) catalyzed by 1,4- (2,5-di-p-methoxyphenyl) squaramide tetrabutyl ammonium catalyst (Sq 3A 3).
In this example, the formula of the ring-opening polymerization reaction of Levorotatory Lactide (LLA) is as follows.
The method for preparing poly-L-lactide (PLLA) by catalyzing ring-opening polymerization of L-lactide (LLA) by the catalyst (Sq 3A 3) is as follows.
200 parts of LLA (2.7mL, 2.0 mmol) and 1 part of NtA (200. Mu.L,0.01 mmol) and 1 part of Sq3A3 catalyst (50. Mu.L, 0.01 mmol) are added to a dry vessel and reacted for 15min at room temperature, 0.5mL of acetic acid is added to terminate the reaction, and a small amount of the crude product is taken for SEC and 1 and H NMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer. The final product was collected and dried in a vacuum oven at 40 ℃ overnight.
According to SEC and 1 as a result of HNMR, the conversion of LLA was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 28.8kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 37.4kg/mol, 1 number average molecular weight (M) calculated by HNMR n,NMR ) 30.8kg/mol, molecular weight distribution
Was 1.09.
Example 22
This example is the ring-opening polymerization of LLA catalyzed by 1,4- (3,4,5-tri-p-methoxyphenyl) squaramide tetrabutyl amine catalyst (Sq 4A 3).
In this example, the reaction formula of LLA ring-opening polymerization is as follows.
In this example, the catalyst (Sq 4A 3) catalyzes the LLA ring-opening polymerization to prepare PLLA as follows.
This example was carried out in the same manner as in example 11 except that the lactide was changed to L-lactide and the initiator was changed to 1,1,1-trihydroxypropane, the reaction was terminated by adding 0.5mL of acetic acid after 2min at room temperature, and a small amount of the crude product was taken out and subjected to SEC and SEC 1 HNMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer. The final product was collected and dried in a vacuum oven at 40 ℃ overnight.
According to SEC and 1 as a result of H NMR, the conversion of LLA was 88%, and the theoretical number average molecular weight (M) was calculated n,th ) 9.5kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 12.3kg/mol, 1 number average molecular by H NMR calculationQuantity (M) n,NMR ) 11.0kg/mol, molecular weight distribution
Is 1.04.
Example 23
This example is 1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) catalyzed ring-opening copolymerization of ε -CL and L-lactide (LLA).
In this example, the ring-opening copolymerization reaction formula of Levorotatory Lactide (LLA) is as follows.
In this example, the ring-opening copolymerization method of ε -CL and L-lactide (LLA) catalyzed by the catalyst (Sq 5A 3) is as follows.
100 parts of ε -CL (1.0 mL, 9mmol) and 1 part of NtA (90. Mu.L, 0.09 mmol) and 1 part of Sq5A3 catalyst (0.45mL, 0.09mmol) were put into a dry container under an inert gas atmosphere, and after 1 hour at room temperature, a small amount of the crude product was subjected to SEC and SEC 1 H NMR measurement.
According to SEC and 1 as a result of H NMR, conversion of ε -CL was 86%, and number average molecular weight (M) was measured by SEC n,SEC ) Is 12.8kg/mol, 1 h NMR calculated number average molecular weight of 10.3kg/mol, molecular weight distribution
Was 1.07.
Then, 75 parts of LLA (1.0 mL, 0.75mmol) was added thereto and reacted at room temperature for 1min, 0.5mL of acetic acid was added thereto to terminate the reaction, and a small amount of the crude product was subjected to SEC and 1 and H NMR test. The remaining crude product was poured into 20mL of methanol to precipitate the polymer. The final product was collected and dried in a vacuum oven at 40 ℃ overnight.
According to SEC and 1 as a result of H NMR, the conversion of LA was 100%, and the number average molecular weight (M) was measured by SEC n,SEC ) Is 28.4kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 21.8kg/molMolecular weight distribution
Is 1.14.
Example 24
This example is 1,4-tetrabutylammonium diphenylsquaramide catalyst (Sq 1A 3) catalyzed LA ring opening polymerization.
35 parts of LA (0.47mL, 0.35mmol) and 1 part of NtA (200. Mu.L, 0.01 mmol) and 1 part of Sq1A3 (50. Mu.L, 0.01 mmol) as a catalyst were put in a dried container under an inert gas atmosphere, reacted at room temperature for 5min, then 0.5mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was subjected to SEC and SEC 1 And H NMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
In the example, the SEC curve of the purified product prepared by the lactide ring-opening polymerization catalyzed by the catalyst Sq1A3, 1 HNMR spectra and MALDI-TOF spectra, shown in fig. 7, fig. 8 and fig. 9, respectively, wherein: FIG. 9 (a) is a MALDI-TOF spectrum of a purified product, and FIG. 9 (b) is an enlarged view of a dotted line portion in FIG. 9 (a).
See FIGS. 7-9, according to SEC and 1 as a result of H NMR, the conversion of LA was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 4.9kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 7.2kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 5.1kg/mol, molecular weight distribution
Was 1.05.
Example 25
This example shows the alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by 1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3).
In this example, the reaction formula of alternating copolymerization of propylene oxide and phenyl isothiocyanate is as follows.
In the present example, the method of catalyzing the alternating copolymerization of propylene oxide and phenyl isothiocyanate by the catalyst Sq5A3 is as follows.
Catalyst Sq5A3 is insoluble in any solvent, and 100 parts of phenyl isothiocyanate (1.6 mL,13.4 mmol), 150 parts of propylene oxide (1.4 mL, 20mmol) and 1 part of cis-butenediol (268. Mu.L, 0.134 mmol) are charged directly into a Schlenk flask under an atmosphere of inert conditions. After 26h of reaction at room temperature, 0.5mL of acetic acid was added to stop the reaction, and a small amount of the crude product was taken for SEC and SEC 1 HNMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
SEC Curve of purified product prepared by alternate copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by Sq5A3 and 1 HNMR spectra, as shown in fig. 10 and fig. 11, respectively.
See FIGS. 10 and 11, in terms of SEC and 1 as a result of H NMR, the conversion of phenylisothiocyanate was 75%, and the theoretical number average molecular weight (M) was calculated n,th ) 14.5kg/mol, number average molecular weight (M) by SEC n,SEC ) The weight ratio of the total amount of the catalyst to be used was 11.8kg/mol, 1 number average molecular weight (M) calculated by HNMR n,NMR ) 11.8kg/mol, molecular weight distribution
It was 1.07.
Example 26
This example shows the alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by 1,4-bis (4-p-methoxyphenyl) squaramide tetrabutylammonium catalyst (Sq 2A 3).
In this example, an ionic catalyst Sq2A3 was dissolved in DMSO to prepare a 0.2mol/L catalyst solution. Then, 30 parts of phenyl isothiocyanate (0.8mL, 6.7mmol), 45 parts of propylene oxide (0.7mL, 10mmol), 1 part of cis-butenediol (450. Mu.L, 0.225 mmol) and 0.1 part of Sq5A3 (0.0225 mmol) were put into a dry vessel under inert conditions, reacted at room temperature for 36 hours, and then 0.5mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was subjected to SEC and SEC 1 HNMR test.
According to SEC and 1 as a result of HNMR, the conversion of phenylisothiocyanate was 74%, which was calculated to beTheoretical number average molecular weight (M) n,th ) 4.3kg/mol, number average molecular weight (M) by SEC n,SEC ) Is in the range of 3.3kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 2.9kg/mol, molecular weight distribution
Was 1.08.
Example 27
This example is a1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) catalyzed alternating copolymerization of propylene oxide and isopropyl isothiocyanate.
In this example, the alternating copolymerization reaction formula is as follows.
In this example, the alternating copolymerization process of propylene oxide and isopropyl isothiocyanate catalyzed by catalyst (Sq 5A 3) was the same as that in example 26, the catalyst Sq2A3 was replaced by Sq5A3, phenyl isothiocyanate was replaced by isopropyl isothiocyanate, after 48 hours of reaction at room temperature, 0.5mL of acetic acid was added to terminate the reaction, and a small amount of crude product was taken to perform SEC and SEC 1 H NMR measurement. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
SEC Curve of crude product prepared by alternate copolymerization of Sq5A3 catalyzed propylene oxide and isopropyl isothiosulfate 1 HNMR spectra are shown in FIG. 12 and FIG. 13, respectively.
See fig. 12 and 13, in terms of SEC and 1 as a result of H NMR, the conversion of isopropyl isothiocyanate was 98%, and the theoretical number average molecular weight (M) was calculated n,th ) At 4.7kg/mol, the number average molecular weight (M) was determined by SEC n,SEC ) Is in the range of 3.2kg/mol, 1 number average molecular weight (M) calculated by HNMR n,NMR ) 3.2kg/mol, molecular weight distribution
Was 1.08.
Example 28
This example is 1,4-alternating copolymerization of propylene oxide and isothiocyanatoethyl ester catalyzed by dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3).
In this example, the reaction formula of alternating copolymerization is as follows.
In this example, the alternating copolymerization catalyzed by the Sq5A3 catalyst was the same as that in example 26, the Sq2A3 catalyst was replaced by Sq5A3, the phenyl isothiocyanate was replaced by the ethyl isothiocyanate, the reaction was terminated by adding 0.5mL of acetic acid after 96 hours at room temperature, and a small amount of the crude product was subjected to SEC and SEC 1 H NMR measurement. The remaining crude product was poured into 20mL of methanol to precipitate the polymer.
According to SEC and 1 as a result of HNMR, the conversion of ethyl isothiocyanate was 98%, and the theoretical number average molecular weight (M) was calculated n,th ) At 4.2kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 4.4kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 4.7kg/mol, molecular weight distribution
Was 1.14.
Example 29
This example shows the alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq 1A 3).
In the embodiment, the alternating copolymerization method of propylene oxide and phenyl isothiocyanate catalyzed by catalyst Sq1A3 is the same as the operation of embodiment 25, catalyst Sq5A3 is replaced by Sq1A3, after the reaction is carried out for 36 hours at room temperature, 0.5mL of acetic acid is added to stop the reaction, and a small amount of crude product is taken to be subjected to SEC and SEC 1 H NMR measurement. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
According to SEC and 1 as a result of HNMR, the conversion of phenylisothiocyanate was 94%, and the theoretical number-average molecular weight (M) was calculated n,th ) 18.2kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 10.1kg/mol of a polymer, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 19.4kg/mol, molecular weight distribution
Is 1.17.
Example 30
This example is a1,4-alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) at 60 ℃.
In this example, the reaction formula of alternate copolymerization of the catalyst Sq5A3 is as follows.
In this example, the alternate copolymerization method of propylene oxide and phthalic anhydride catalyzed by catalyst Sq5A3 is as follows.
50 parts of phthalic anhydride (1mL, 1mmol), 150 parts of propylene oxide (210. Mu.L, 3 mmol), 1 part of terephthalyl alcohol (40. Mu.L, 0.02 mmol) and 1 part of Sq5A3 catalyst (100. Mu.L, 0.02 mmol) are added to a dried container under inert conditions, the reaction is terminated after 48 hours at 60 ℃, 0.5mL of acetic acid is added, and a small amount of the crude product is subjected to SEC and 1 HNMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
According to SEC and 1 as a result of H NMR, the conversion of phthalic anhydride was 52%, and the theoretical number average molecular weight (M) was calculated n,th ) 5.2kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 2.6kg/mol of a polymer, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 6.6kg/mol, molecular weight distribution
Is 1.25.
Example 31
This example is 1,4-dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3) alternating copolymerization of propylene oxide and phthalic anhydride catalyzed at room temperature.
This example was performed in the same manner as example 30, and was inverted at room temperatureAfter 48h, 0.5mL of acetic acid was added to stop the reaction, and a small amount of the crude product was taken for SEC and 1 h NMR measurement. The remaining crude product was poured into 20mL of methanol to precipitate the polymer.
In this example, the SEC curve of the crude product prepared by alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq5A3 catalyst 1 The H NMR spectra are shown in FIG. 14 and FIG. 15, respectively.
See fig. 14 and 15, in terms of SEC and 1 as a result of H NMR, the conversion of phthalic anhydride was 41%, and the theoretical number average molecular weight (M) was calculated n,th ) At 4.0kg/mol, and a number average molecular weight (M) by SEC n,SEC ) Is 2.3kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 3.7kg/mol, molecular weight distribution
Is 1.26.
Example 32
This example is a1,4-di-tert-butyl squaramide tetrabutylammonium catalyst (Sq 10A 3) catalyzed alternating copolymerization of propylene oxide and phthalic anhydride.
The method for catalyzing the alternating copolymerization of the epoxypropane and the phthalic anhydride by the catalyst (Sq 10A 3) is the same as the operation of the example 30, after the reaction is carried out for 48 hours at the temperature of 60 ℃, 0.5mL of acetic acid is added to stop the reaction, and a small amount of crude product is taken to carry out SEC and SEC 1 And (4) HNMR testing. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
SEC Curve of crude product prepared by alternate copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq10A3 and 1 the H NMR spectra are shown in FIGS. 16 and 17, respectively.
See FIGS. 16 and 17, in accordance with SEC and 1 as a result of H NMR, the conversion of phthalic anhydride was 52%, and the theoretical number average molecular weight (M) was calculated n,th ) 5.2kg/mol, number average molecular weight (M) by SEC n,SEC ) Is in the range of 3.3kg/mol, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 7.8kg/mol, molecular weight distribution
Was 1.13.
Example 33
This example is a1,4-alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by dicyclohexyl squaramide tetrabutylammonium catalyst (Sq 5A 3).
In this example, the reaction formula of alternating copolymerization is as follows.
The styrene oxide and phthalic anhydride alternating copolymerization method catalyzed by the catalyst Sq5A3 is as follows.
20 parts of phthalic anhydride (0.4 mL, 0.04mmol), 740 parts of styrene oxide (1.5 mL,14.8 mmol), 1 part of terephthalyl alcohol (40. Mu.L, 0.02 mmol) and 1 part of Sq5A3 catalyst (100. Mu.L, 0.02 mmol) were charged under inert conditions into a dry vessel, reacted at 60 ℃ for 68 hours, then 0.5mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was subjected to SEC and SEC 1 H NMR measurement. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
SEC Curve of crude product prepared by alternate copolymerization of Sq5A3 catalytic styrene oxide and phthalic anhydride 1 The H NMR spectra are shown in FIGS. 18 and 19, respectively.
See fig. 18 and 19, in terms of SEC and 1 as a result of H NMR, the conversion of phthalic anhydride was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 4.9kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 1.1kg/mol of a polymer, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 2.5kg/mol, molecular weight distribution
Was 1.53.
Example 34
This example is a1,4-tricyclo [3,3,1,1 (3,7) ] decylbenzamide tetrabutylammonium catalyst (Sq 11A 3) catalyzed alternating copolymerization of styrene oxide and phthalic anhydride.
The method for catalyzing styrene oxide and phthalic anhydride alternating copolymerization by the catalyst (Sq 11A 3) is the same as the operation of the embodiment 33, after reacting for 68 hours at the temperature of 60 ℃, 0.5mL of acetic acid is added to stop the reaction, and a small amount of acetic acid is takenThe crude product is subjected to SEC and 1 HNMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
According to SEC and 1 as a result of HNMR, the conversion of phthalic anhydride was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 4.9kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 1.7kg/mol of a polymer, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 4.8kg/mol, molecular weight distribution
Is 1.23.
Example 35
This example is the alternating copolymerization of isopropyl glycidyl ether with phthalic anhydride catalyzed by 1,4-tricyclo [3,3,1,1 (3,7) ] decyltetramide tetrabutylammonium catalyst (Sq 11A 3).
In this example, the reaction formula of alternating copolymerization is as follows.
The procedure of the alternating copolymerization in this example was the same as in example 33, styrene oxide was replaced by isopropyl glycidyl ether, the reaction was terminated by adding 0.5mL of acetic acid after reacting at 60 ℃ for 68 hours, and a small amount of the crude product was subjected to SEC and 1 HNMR test. The remaining crude product was poured into 20mL of methanol to precipitate a polymer.
According to SEC and 1 as a result of HNMR, the conversion of phthalic anhydride was 100%, and the theoretical number average molecular weight (M) was calculated n,th ) 5.3kg/mol, number average molecular weight (M) by SEC n,SEC ) Is 2.7kg/mol of the polymer, 1 number average molecular weight (M) calculated by H NMR n,NMR ) 4.4kg/mol, molecular weight distribution
Is 1.44.
The embodiment shows that the catalyst of the invention has simple synthesis, low cost, simple structure, good catalytic activity and good biological safety; the conversion rate of ring-opening polymerization can quickly reach 100% at normal temperature; in the alternating copolymerization reaction at normal temperature, the conversion rate of the isothiocyanate compound reaches 98 percent, the conversion rate of the phthalic anhydride reaches 100 percent, the catalyst has a large industrial application range, the product has high yield and good purity, and the catalyst has a good application prospect.
The above examples are only preferred embodiments of the present invention, which are intended to illustrate the present invention, but not to limit the present invention, and those skilled in the art should be able to make changes, substitutions, modifications, etc. without departing from the spirit of the present invention.
Claims (10)
1. A squaramide ionic organic catalyst is characterized in that the structural formula of the squaramide ionic organic catalyst is shown as the following formula:
in the formula (I);
y represents N or P;
R 3 ，R 4 ，R 5 ，R 6 each represents four independent hydrocarbon groups having 1 to 12 carbon atoms;
R 1 and R 2 Each independently selected from C1-C10 linear alkyl, cyclohexyl, tertiary butyl, isopropyl, allyl, phenyl, naphthyl and R 7 -phenyl or R 7 -a naphthyl group; the R is 7 is-F, -Cl, -Br, -CF 3 、-OCH 3 At least one substituent of alkyl and N, N-disubstituted alkyl.
2. A method for synthesizing the squaramide-type ionic organic catalyst according to claim 1, wherein the method comprises the following steps:
uniformly mixing the compound A, the compound B and an organic solvent, reacting for 2-4 h under the vacuum condition of the pressure of 0.01-1 mbar, and then performing dehydration reaction at 70-80 ℃ to obtain a solid product, namely the squaramide ionic organic catalyst;
the molar ratio of the compound A to the compound B is (1-10): 1, and the dosage ratio of the compound B to the organic solvent is 0.5mmol:15ml;
the structural formula of the compound A is shown as the formula (1):
in the above formula, R 1 And R 2 Each independently selected from C1-C10 straight-chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl and R 7 -phenyl or R 7 -a naphthyl group; the R is 7 is-F, -Cl, -Br, -CF 3 、-OCH 3 At least one substituent of alkyl and N, N-disubstituted alkyl;
the structural formula of the compound B is shown as the formula (2):
in the above formula, Y represents N or P; r is 3 ，R 4 ，R 5 ，R 6 Each represents four independent hydrocarbon groups having 1 to 12 carbon atoms.
3. The method of synthesis according to claim 2, wherein the organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, toluene or acetonitrile.
4. Use of the squarylium amide ionic organic catalyst according to claim 1 in ring-opening polymerization of cyclic ester monomers or cyclic carbonate monomers.
5. Use of the squarylium amide ionic organic catalyst according to claim 1 in alternating copolymerization of an epoxy compound and an isothiocyanate compound.
6. Use of the squarylium amide ionic organic catalyst according to claim 1 in alternating copolymerization of an epoxy compound and phthalic anhydride.
7. The use of claim 4 or 5 or 6, wherein the reaction conditions for the use are: the temperature is 20-60 ℃, and the time is 5 min-68 h.
8. The use of claim 4, wherein the cyclic ester monomer is epsilon-caprolactone, delta-valerolactone, racemic lactide, levolactide, dextrolactide or delta-alkyl valerolactone of C1 to C12; the cyclic carbonate monomer is trimethylene carbonate.
9. The use according to claim 5 or 6, wherein the epoxy compound is ethylene oxide, C1-C20 linear alkyl ethylene oxide, C1-C16 linear alkyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, glycidyl methacrylate, cyclohexene oxide, 4-vinyl cyclohexene oxide or limonene oxide.
10. The use of claim 5, wherein the isothiocyanate compound is at least one of methyl isothiocyanate, linear alkyl isothiocyanate, alicyclic isothiocyanate, isopropyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, benzyl isothiocyanate, phenyl isothiocyanate, o/m/p-toluene isothiocyanate, benzoyl isothiocyanate, chloroethyl isothiocyanate, cyclohexylmethyl isothiocyanate, and allyl isothiocyanate; the carbon atom number of the straight-chain alkyl is 2-20, and the carbon atom number of the alicyclic ring in the alicyclic isothiocyanate is 3-12.
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| JP2003277510A (en) * | 2002-03-22 | 2003-10-02 | Sumitomo Bakelite Co Ltd | Manufacturing method of latent catalyst |
| US20130245268A1 (en) * | 2012-03-13 | 2013-09-19 | The Provost, Fellows, Foundation Scholars, And The Other Members Of Board | Enantioselective organic anhydride reactions |
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