CN114308120A - Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof - Google Patents
Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114308120A CN114308120A CN202111661001.7A CN202111661001A CN114308120A CN 114308120 A CN114308120 A CN 114308120A CN 202111661001 A CN202111661001 A CN 202111661001A CN 114308120 A CN114308120 A CN 114308120A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- organic
- amphiphilic
- phosphorus salt
- organic catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 23
- -1 polythiocarbonate Polymers 0.000 claims abstract description 47
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000003384 small molecules Chemical class 0.000 claims abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012372 hydroboration reagent Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical group 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 150000004714 phosphonium salts Chemical class 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000006197 hydroboration reaction Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 150000002540 isothiocyanates Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 150000001540 azides Chemical class 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 229920000728 polyester Polymers 0.000 abstract description 14
- 229920000515 polycarbonate Polymers 0.000 abstract description 12
- 239000004417 polycarbonate Substances 0.000 abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 10
- 229920000570 polyether Polymers 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 230000000269 nucleophilic effect Effects 0.000 abstract description 5
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- 229920006295 polythiol Polymers 0.000 abstract description 3
- 229920005604 random copolymer Polymers 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 150000002596 lactones Chemical class 0.000 abstract description 2
- 239000012434 nucleophilic reagent Substances 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 9
- 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 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 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 description 6
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 6
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 6
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 5
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 5
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 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 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 3
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- OQOIYECUXDNABI-UHFFFAOYSA-N 2-phenylthiirane Chemical compound C1SC1C1=CC=CC=C1 OQOIYECUXDNABI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 239000002253 acid Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 125000005592 polycycloalkyl group Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical compound NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 description 1
- 102100029272 5-demethoxyubiquinone hydroxylase, mitochondrial Human genes 0.000 description 1
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical group C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000028 Gradient copolymer Polymers 0.000 description 1
- 101000770593 Homo sapiens 5-demethoxyubiquinone hydroxylase, mitochondrial Proteins 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- AZSYUHSAQICHNK-UHFFFAOYSA-N [C]=O.[S] Chemical group [C]=O.[S] AZSYUHSAQICHNK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- OCDXZFSOHJRGIL-UHFFFAOYSA-N cyclohexyloxycyclohexane Chemical compound C1CCCCC1OC1CCCCC1 OCDXZFSOHJRGIL-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a phosphorus salt amphiphilic dual-functional organic catalyst and a preparation method and application thereof, belonging to the field of synthesis and application of organic catalysts. The invention solves the problem that the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing two or more components of nucleophilic reagent and electrophilic reagent and even adding a cocatalyst or an initiator. The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention mixes nucleophilic electrophilic groups and initiating species into a catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids the use of a complex multicomponent catalytic system. The catalyst can be used for the preparation of high molecular materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like, and the synthesis of block or random copolymers thereof, can also be used for carrying out organic small molecule coupling reaction to prepare fine chemicals such as cyclic carbonate, lactone and thio-cyclic carbonate, and has the characteristics of high efficiency, high selectivity, controllability and the like.
Description
Technical Field
The invention relates to a phosphorus salt amphiphilic dual-functional organic catalyst, and a preparation method and application thereof, and belongs to the field of synthesis and application of organic catalysts.
Background
Organic catalysts have attracted attention of researchers due to low cost, easy availability, low biotoxicity and the like, but compared with the application of organic catalysts in organic methodology, organic catalysts are still in the infancy stage in the field of polymer synthesis and preparation, and currently prepared polymer materials comprise: polyesters, polycarbonates, polyethers, polyamides, polysiloxanes, polyurethanes, and the like.
Currently, the commonly used organic catalytic systems mainly comprise the following types: carboxylic acid catalytic systems, pyridine base catalytic systems, nitrogen heterocyclic carbene catalytic systems, nitrogen-containing organic base (guanidino, amidino, amine) catalytic systems, thiourea/urea + amine or thiourea/urea + base (organic strong base or other bases), phosphazene base catalytic systems, etc., which have been used for preparing polycarbonate from alkylene oxide and carbon dioxide, preparing polyester from alkylene oxide and epoxy anhydride, preparing polyether from alkylene oxide by ring-opening polymerization, preparing polyester high molecular material from cyclic lactone by ring-opening polymerization, preparing polycarbonate from cyclic carbonate by ring-opening polymerization, obtaining polyamide from lactam by ring-opening polymerization, preparing polysiloxane from cyclic siloxane by ring-opening polymerization, catalyzing (meth) acrylate polymerization to obtain poly (meth) acrylate, and catalyzing vinyl ether polymerization to obtain functionalized polyethylene.
The polymerization mechanism mainly includes: electrophilic activation of monomer, nucleophilic activation of initiator, synergistic activation of monomer and initiator, and the like. Thiourea/urea + organic bases, phosphazene bases, carbenes and nitrogen-containing organic bases have been reported in literature as ring-opening polymerization of cyclic lactone, alkylene oxide, epoxy silane, cyclic carbonate and other monomers, and active species are obtained by activating an initiator to initiate polymerization reaction, so as to realize chain growth.
The onium salt can be used in polymerization reaction with Lewis acid trialkyl boron to construct acid-base pair or phosphonitrile/alcohol/trialkyl boron to construct multi-component catalytic system. Trialkylboron is used as Lewis acid and electrophilic reagent, can activate monomer to stabilize the chain end of active species of polymer, onium salt and phosphazene/alcohol have nucleophilicity as initiator, and the bi-component or multi-component system can effectively improve the activity and controllability of polymerization reaction. The triethylboron and the phosphazene compounds are used for ring-opening polymerization of alkylene oxide, copolymerization of carbon dioxide and alkylene oxide to prepare polycarbonate, copolymerization of alkylene oxide and heteroatom allene to prepare polycarbonate, copolymerization of epoxy and acid anhydride to prepare polyester and the like as reported in the literature.
However, the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing two or more components of nucleophilic reagent and electrophilic reagent or even adding a cocatalyst or an initiator, which brings difficulty to the reagent operation, accuracy and mechanistic research of the polymerization reaction; the weighing and quantity of the multiple components adds to the error of the experimental operation.
Disclosure of Invention
The invention provides a phosphorus salt amphiphilic dual-functional organic catalyst, a preparation method and application thereof, aiming at solving the problems in the prior art.
The technical scheme of the invention is as follows:
a phosphorus salt amphiphilic dual-functional organic catalyst has the following structural formula:
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1; y isWherein R is1、R2And R3Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.
Further defined, Y is BR3 and the organic catalyst is of the structure:
n is an integer of 1 or more, and the kind of the chain is not limited to a carbon chain, but may be other heteroatom carbon chains containing heteroatoms such as Si, N, O, P, S; BR (BR)3Being cyclic boranes or aliphatic or aromatic boranes, R3The structure of (A) is as follows:
Further, X is a combination of two or more of a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a hydroxide ion, a nitrate ion, an azide ion, a tetrafluoroborate anion, a lithium tetrakis (pentafluorophenyl) borate anion, a nickel tetracarbonyl anion, a carbonate ion, a sulfonate ion, a phosphate ion, a hypochlorite ion, a carboxylate ion, an alkoxide ion, and a phenoxide ion.
More particularly, the organic catalyst is of the structure:
further, the substituents on the phosphine are not limited to benzene rings, and can be substituents of 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or multi-ring bridged benzene rings.
Further defined, PhO-May be a mono-substituted phenol or a poly-substituted phenol.
Further, the length of the carbon chain is not limited to 3, and an integer greater than 3 may be used.
Further defined, the organic catalyst has the following structure:
further, the substituents on the phosphine are not limited to methyl, but may be ethyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, or methyl 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or other polycycloalkyl and substituted polycycloalkyl substituents.
Further defined, PhO-May be a mono-substituted phenol or a poly-substituted phenol.
Further, the length of the carbon chain is not limited to 3, and an integer greater than 3 may be used.
The amphiphilic bifunctional phosphorus salt is prepared by carrying out hydroboration reaction on SM containing two unsaturated double bonds and a hydroboration reagent containing at least one boron hydrogen bond.
Further limited, the preparation method of the organic catalyst comprises the following steps: mixing SM and a hydroboration reagent in an inert atmosphere, adding an organic solvent, stirring for 1-144 h at-78-100 ℃, and removing organic matters and impurities after the reaction is finished to obtain the phosphorus salt amphiphilic dual-functional organic catalyst.
Further defined, the molar ratio of quaternary phosphonium salt to hydroboration reagent in SM is 1: (2-3).
More particularly, the structure of the SM is as follows:
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Bonded or cyclized by a covalent bond.
Further, N is an integer of 1 or more, and the kind of the chain is not limited to a carbon chain, and may be other heteroatom carbon chains including heteroatoms such as Si, N, O, P, and S.
In a further definition, R1、R2And R3Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.
More specifically, X is a combination of two or more of fluoride ion, chloride ion, bromide ion, iodide ion, hydroxide ion, nitrate ion, azide ion, tetrafluoroborate anion, lithium tetrakis (pentafluorophenyl) borate anion, nickel tetracarbonyl anion, carbonate ion, sulfonate ion, phosphate ion, hypochlorite ion, carboxylate ion, alkoxide ion, and phenoxide ion.
More particularly, the hydroboration reagent is a cyclic, aliphatic or aromatic borane containing one or a combination of two or more of the following structures:
More particularly, the hydroboration reagent is 9-borabicyclo (3,3,1) -nonane.
Further, the organic solvent is one or more of tetrahydrofuran, benzene, toluene, chloroform, dichloromethane, hexane, diethyl ether, carbon tetrachloride, N-dimethylformamide, ethyl acetate, and 1, 4-dioxane, and is mixed in an arbitrary ratio.
The phosphorus salt amphiphilic dual-functional organic catalyst is applied to preparation of organic micromolecules or high molecular materials, wherein the organic micromolecules or the high molecular materials are obtained by ring opening polymerization reaction of one or more than two cyclic monomers under the action of the catalyst, or are obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isothiocyanate, isocyanate or carbon monoxide under the action of the catalyst.
Further limiting, the specific application method is as follows: mixing a catalyst and a cyclic monomer according to a molar ratio of 1: (200-10000) and reacting for 0.16-6 h at-40-25 ℃, wherein the molecular weight of the obtained polymer is within the range of 1-4640 kg/mol, and the molecular weight distribution isIn the range of 1.02 to 1.3.
Further defined, the cyclic monomer comprises one or a combination of more than one of the following structures:
further limiting, the organic small molecule product is carbon dioxide/carbon disulfide and alkylene oxide/episulfide alkane which are subjected to catalytic coupling reaction by a catalyst to obtain cyclic carbonate.
Further limiting, the organic micromolecule product is cyclic lactone obtained by catalytic coupling reaction of CO and alkylene oxide through a catalyst.
Further limiting, the organic small molecule product is sulfur carbon oxide and alkylene oxide/episulfide alkane which are catalyzed and coupled by a catalyst to obtain cyclic thiocarbonate.
More limited, the polymer is aliphatic polycarbonate or polyether obtained by catalytic copolymerization of carbon dioxide and alkylene oxide through a catalyst.
Further limited, the polymer is polyether obtained by catalyzing ring-opening polymerization of alkylene oxide by a catalyst; the polythioether is obtained by the ring-opening polymerization of the episulfide under the catalysis of a catalyst; polyester obtained by catalyzing alkylene oxide and cyclic anhydride by a catalyst; polyester obtained by catalyzing poly-heteroatom carbonate obtained by copolymerizing heteroatom allene and heteroatom cyclic compound by using a catalyst; the polyester is obtained by catalytic polymerization of alkylene oxide and carbon monoxide in the presence of a catalyst.
More particularly, polyether-polyester, polyester-polycarbonate, polyether-polycarbonate diblock, triblock, multiblock, gradient, or random copolymers are prepared by adjusting the order of addition of alkylene oxide, anhydride, cyclic lactone, carbon dioxide.
More particularly, the organic catalysts CAT1-CAT6 and CAT13-CAT18 are used for catalyzing homopolymerization or copolymerization of Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), epoxycyclohexyl (CHO), Limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) to obtain polyether, or used for catalyzing copolymerization of Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), epoxycyclohexyl (CHO), Limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) and CO2 to obtain polycarbonate or cyclic carbonate.
More particularly, the organic catalysts CAT1-CAT6 and CAT13-CAT18 are used to catalyze the copolymerization of Ethylene Oxide (EO), Propylene Oxide (PO), Butylene Oxide (BO), cyclohexyl oxide (CHO), Limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) with cyclic Maleic Anhydride (MA), Succinic Anhydride (SA), Diethylene Glycol Anhydride (DGA) or Phthalic Anhydride (PA) to give polyesters.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing EO, PO, BO or AGE homopolymerization or copolymerization to obtain polyether, and the polymerization reaction is active polymerization.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing ring-opening polymerization or copolymerization of Lactide (LA), beta-butyrolactone (beta-BL), gamma-butyrolactone (gamma-BL), delta-valerolactone (delta-VL) or epsilon-caprolactone (epsilon-CL) to obtain the polyester.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing the copolymerization of Ethylene Sulfide (ES), Propylene Sulfide (PS), cyclohexane sulfide (CHS) and carbon dioxide to obtain polythiocarbonate; or for catalyzing 2-phenylthiirane (SS) or PS with CO2Copolymerization to obtain cyclic thiocarbonate.
More particularly, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing the copolymerization of Propylene Oxide (PO) with carbon oxysulfide to obtain polythiocarbonate, or for catalyzing the copolymerization of Ethylene Sulfide (ES) with carbon oxysulfide or carbon disulfide to obtain polythiocarbonate, or for catalyzing the copolymerization of Propylene Oxide (PO) with carbon disulfide to obtain polyether.
More specifically, when the organic catalyst is used for preparing the polymer, the preparation can be carried out in the presence of a chain transfer agent, so that the molecular weight of the prepared polymer can be regulated (both high and low molecular weight polymers can be prepared), the dosage of the catalyst is reduced, the molecular weight distribution of the polymer is reduced, and the polymer with functional terminal functional groups (such as ester groups, phenol groups, amino groups, hydroxyl groups, azide groups and the like) is prepared.
More particularly, the method comprises the steps of adding one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyols and water into a polymerization reaction system to serve as a chain transfer agent to prepare corresponding polymer polyols or poly-thiol; or adding one or more polymers with alcoholic hydroxyl, phenolic hydroxyl, amino and carboxyl as macromolecular chain transfer agents into a polymerization reaction system to prepare the corresponding block copolymer or graft copolymer.
Further defined, the chain transfer agent comprises one or a combination of more than one of the following structures:
whereinRepresents the main chain of a macromolecular chain transfer agent, andthe alcoholic hydroxyl group, phenolic hydroxyl group, amino group or carboxylic acid group shown in the main chain does not represent the actual number of functional groups, and the actual number is an arbitrary integer of 1 or more.
Further, in the preparation of the polymer by the organic catalyst, a Lewis acid, a Lewis base, or other multi-component catalyst or cocatalyst may be added to the polymerization system.
The phosphorus salt amphiphilic dual-functional organic catalyst is loaded on inorganic or organic substances and used for preparing organic micromolecules or high molecular materials, so that the catalyst can be recycled, and the loss of the catalyst to the maximum extent is avoided.
The invention has the following beneficial effects:
(1) the phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention mixes nucleophilic electrophilic groups and initiating species into a catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids the use of a complex multicomponent catalytic system.
(2) The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention also has the characteristics of definite structure, accurate components and synergistic catalysis, which is difficult to achieve by the conventional diversified system.
(3) The preparation method of the phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention has the characteristics of easily available raw materials, short and simple synthetic route and the like.
(4) The organic catalyst with double functions of phosphorus salt amphipathy provided by the invention is used for preparing high polymer materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like and synthesizing a block or random copolymer thereof, can also be used for preparing fine chemicals such as cyclic carbonate, lactone and thio-cyclic carbonate by carrying out organic micromolecule coupling reaction, and has the characteristics of high efficiency, high selectivity, controllability and the like.
Drawings
FIG. 1 is a drawing of CAT11H NMR spectrum;
FIG. 2 shows CAT21H NMR spectrum;
FIG. 3 of pure PPO1H NMR spectrum;
FIG. 4 is a GPC chart of Effect example 1;
FIG. 5 is a drawing of Poly (AGE)1H NMR spectrum;
FIG. 6 is of Poly (BO)1H NMR spectrum.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1
The synthesis of catalyst CAT1 is as follows:
the preparation process comprises the following steps:
in a flame-dried Schlenk vessel, diallyl diphenyl phosphine bromide (173.6mg, 0.5mmol, 1 eq.) and 9-borabicyclo [3.3.1 ]]Nonane (9-BBN) (122mg, 1.0mmol, 2.0 equiv.) is dissolved in 10mL of chloroform. The reaction mixture was allowed to stir at 80 ℃ for 12 hours. Removing all volatiles and washing the resulting with hexaneWhite solid 3 times (10mL) to give the desired product in quantitative yield1The H NMR spectrum is shown in FIG. 1 (400MHz, CDCl)3,298K)。
Example 2
The synthesis of catalyst CAT2 is as follows:
the preparation process comprises the following steps:
in a flame-dried Schlenk vessel, diallyl diphenyl phosphine iodide (307mg, 0.78mmol, 1 eq.) and 9-borabicyclo [3.3.1 ] were placed]Nonane (9-BBN) (190.4mg, 1.56mmol, 2 equiv.) is dissolved in 10mL CHCl3In (1). The reaction mixture was allowed to stir at 80 ℃ for 12 hours. All volatiles were removed and the resulting white solid was washed 3 times with hexanes (10mL) to give the desired product in quantitative yield, product1The H NMR spectrum is shown in FIG. 2 (400MHz, CDCl)3,298K)。
Example 3
The synthesis of catalyst CAT4 is as follows:
the preparation process comprises the following steps:
CAT1(118.3mg, 0.2mmol, 1 equiv.) and sodium benzoate (115.3mg, 0.8mmol, 4 equiv.) were dissolved in 8ml of CHCl in a flame-dried Schlenk vessel3In (1). The reaction mixture was allowed to stir at room temperature for 48 hours. Filtering under nitrogen atmosphere to collect filtrate, and removing all volatile componentsThe resulting white oil was washed 3 times with hexane (10mL) to obtain the desired white quantitative product.
Example 4
The synthesis of catalyst CAT5 is as follows:
the preparation process comprises the following steps:
CAT1(118.3mg, 0.2mmol, 1 equiv.) and sodium acetate (65.6mg, 0.8mmol, 4 equiv.) were dissolved in 8ml of chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under a nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times with hexane (10mL) to obtain the desired white quantitative product.
Example 5
The synthesis of catalyst CAT6 is as follows:
the preparation process comprises the following steps:
CAT1(118.3mg, 0.2mmol, 1 equiv.) and sodium trifluoroacetate (108.8mg, 0.8mmol, 4 equiv.) were dissolved in 8ml of chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under a nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times with hexane (10mL) to obtain the desired white quantitative product.
Effect example 1
The catalyst CAT1-CAT6 is used for catalyzing the homopolymerization of the propylene oxide, and the synthetic route is as follows:
the preparation process comprises the following steps:
in a glove box, weighing PO and a catalyst into a small bottle of a pressure-resistant bottle which is provided with a magnetic stirrer and is flame-dried in advance and is 5mL, taking out the small bottle in a sealed mode, setting the temperature to be 20-25 ℃ as a reaction temperature, controlling the molar ratio of the PO to the catalyst to be 200: 1-10000: 1, and controlling the reaction time to be 10-120 min. The key data of application examples 1-12 are collated in Table 1.
Effect example 2
Catalyst CAT1-CAT6 is used for catalyzing alkylene oxide and CO2The copolymerization reaction is carried out by the following synthetic route:
the preparation process comprises the following steps:
in a glove box, alkylene oxide and a catalyst are added into a reaction kettle, the reaction kettle is flushed with carbon dioxide with certain pressure, the reaction is carried out under the set temperature condition, and the monomer conversion rate and the selectivity of the product (the proportion of polycarbonate, polyether and cyclic carbonate) are represented by nuclear magnetism. The key data of application examples 13-36 are collated in tables 2-5.
TABLE 2
TABLE 3
TABLE 4
TABLE 5
Effect example 3
The catalyst CAT1-CAT6 is used for catalyzing the copolymerization of alkylene oxide and cyclic anhydride, and the synthetic route is as follows:
the preparation process comprises the following steps:
in a glove box, taking a proper amount of cyclic anhydride, alkylene oxide and a catalyst, placing the cyclic anhydride, the alkylene oxide and the catalyst in a pressure-resistant bottle, and reacting for 10min-12h at the temperature of 60-180 ℃. Taking reaction liquid to test nuclear magnetism to characterize monomer conversion rate and selectivity of products. Precipitated from methanol, filtered and dried, and the polymer was analyzed by GPC. The key data of application examples 37 to 53 are summarized in tables 6 to 7.
TABLE 6
TABLE 7
Effect example 4
The catalyst CAT1-CAT6 is used for catalyzing the homopolymerization of the cyclic lactone, and the synthetic route is as follows:
the preparation process comprises the following steps:
in a glove box, adding a proper amount of cyclic lactone monomer and a catalyst into a pressure-resistant bottle, adding a certain amount of organic solvent, and reacting for 2-12h at the temperature of-10-80 ℃. Taking reaction liquid, testing the conversion rate of nuclear magnetism characterization monomers and the selectivity of the product, filtering the polymer, drying to obtain a polyester target product, and performing GPC test analysis on the polyester target product. The key data of application examples 54 to 55 are collated in Table 8.
TABLE 8
Effect example 5
The catalyst CAT7-CAT24 is used for catalyzing the homopolymerization of the cyclic lactone, and the synthetic route is as follows:
the catalysts CAT7-CAT24 were prepared in the same manner as CAT1-CAT 6.
The preparation process comprises the following steps:
in a glove box, a proper amount of propylene oxide monomer and a catalyst are added into a pressure-resistant bottle and react for 2 to 12 hours at the temperature of between 25 and 100 ℃. Taking reaction liquid, and testing the conversion rate of nuclear magnetism characterization monomers and the selectivity of products. The key data of application examples 56-61 are collated in Table 9.
TABLE 9
Claims (10)
1. A phosphorus salt amphiphilic dual-functional organic catalyst is characterized in that the structural formula of the organic catalyst is as follows:
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1; y isWherein R is1、R2And R3Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.
3. The phosphonium salt amphiphilic bifunctional organic catalyst as claimed in claim 1, wherein X is a combination of two or more of fluoride, chloride, bromide, iodide, hydroxide, nitrate, azide, tetrafluoroborate, lithium tetrakis (pentafluorophenyl) borate, nickel tetracarbonyl, carbonate, sulfonate, phosphate, hypochlorite, carboxylate, alkoxide, phenoxide.
5. the preparation method of the amphiphilic bifunctional organic phosphorus salt catalyst as claimed in any one of claims 1 to 4, wherein the organic phosphorus salt catalyst is obtained by carrying out a hydroboration reaction on SM containing two unsaturated double bonds and a hydroboration reagent containing at least one boron hydrogen bond;
the structure of the SM is as follows:
wherein X is an anion, R1And R2Are identical or different substituents, or R1And R2Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1;
the hydroboration reagent is ring, aliphatic or aromatic borane containing one or more than two of the following structures:
6. The method for preparing the amphiphilic bifunctional organic catalyst containing phosphorus salt as claimed in claim 5, wherein the method for preparing the organic catalyst comprises: mixing SM and a hydroboration reagent in an inert atmosphere, adding an organic solvent, stirring for 1-144 h at-78-100 ℃, and removing organic matters and impurities after the reaction is finished to obtain the phosphorus salt amphiphilic dual-functional organic catalyst;
the organic solvent is one or more than two of tetrahydrofuran, benzene, toluene, chloroform, dichloromethane, hexane, diethyl ether, carbon tetrachloride, N-dimethylformamide, ethyl acetate and 1, 4-dioxane which are mixed in any proportion.
7. The application of the phosphorus salt amphiphilic dual-functional organic catalyst in preparation of organic micromolecules or high molecular materials according to any one of claims 1 to 4 is characterized in that the organic micromolecules or high molecular materials are obtained by ring opening polymerization reaction of one or more than two cyclic monomers under the action of a catalyst, or are obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isothiocyanate, isocyanate or carbon monoxide under the action of a catalyst;
the specific application method comprises the following steps: mixing a catalyst and a cyclic monomer according to a molar ratio of 1: (200-10000) and reacting for 0.16-6 h at-40-25 ℃.
9. the use of the phosphorus salt amphiphilic bifunctional organic catalyst as claimed in claim 7, wherein the catalyst is used for preparing polymer in the presence of chain transfer agent; the chain transfer agent comprises one or more of the following structures:
whereinRepresents the main chain of a macromolecular chain transfer agent, andthe alcoholic hydroxyl group, phenolic hydroxyl group, amino group or carboxylic acid group shown in the main chain does not represent the actual number of functional groups, and the actual number is an arbitrary integer of 1 or more.
10. The phosphorus salt amphiphilic bifunctional organic catalyst as claimed in claim 1 is loaded on inorganic or organic substances for preparing organic small molecule or high molecular material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111661001.7A CN114308120B (en) | 2021-12-30 | 2021-12-30 | Phosphorus salt amphiphilic double-functional organic catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111661001.7A CN114308120B (en) | 2021-12-30 | 2021-12-30 | Phosphorus salt amphiphilic double-functional organic catalyst and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114308120A true CN114308120A (en) | 2022-04-12 |
CN114308120B CN114308120B (en) | 2024-10-01 |
Family
ID=81019819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111661001.7A Active CN114308120B (en) | 2021-12-30 | 2021-12-30 | Phosphorus salt amphiphilic double-functional organic catalyst and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114308120B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114716481A (en) * | 2022-05-10 | 2022-07-08 | 青岛科技大学 | Catalyst and preparation method of functionalized polyether polyol |
CN114716660A (en) * | 2022-05-10 | 2022-07-08 | 青岛科技大学 | Method for preparing catalyst and dihydroxy terminated polyether polyol |
CN115260241A (en) * | 2022-05-10 | 2022-11-01 | 青岛科技大学 | Organic catalyst, polyester polyol and preparation method of polycarbonate polyol |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160108181A1 (en) * | 2013-05-17 | 2016-04-21 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
CN109096481A (en) * | 2018-08-28 | 2018-12-28 | 浙江大学 | A kind of preparation method of the catalyst system for being used to prepare the polymer containing polyethers and a variety of polymer containing polyethers |
CN110938087A (en) * | 2018-09-21 | 2020-03-31 | 浙江大学 | Organic metal-free catalyst with electrophilic nucleophilic bifunctional, preparation method and application thereof |
-
2021
- 2021-12-30 CN CN202111661001.7A patent/CN114308120B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160108181A1 (en) * | 2013-05-17 | 2016-04-21 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
CN109096481A (en) * | 2018-08-28 | 2018-12-28 | 浙江大学 | A kind of preparation method of the catalyst system for being used to prepare the polymer containing polyethers and a variety of polymer containing polyethers |
CN110938087A (en) * | 2018-09-21 | 2020-03-31 | 浙江大学 | Organic metal-free catalyst with electrophilic nucleophilic bifunctional, preparation method and application thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114716481A (en) * | 2022-05-10 | 2022-07-08 | 青岛科技大学 | Catalyst and preparation method of functionalized polyether polyol |
CN114716660A (en) * | 2022-05-10 | 2022-07-08 | 青岛科技大学 | Method for preparing catalyst and dihydroxy terminated polyether polyol |
CN115260241A (en) * | 2022-05-10 | 2022-11-01 | 青岛科技大学 | Organic catalyst, polyester polyol and preparation method of polycarbonate polyol |
Also Published As
Publication number | Publication date |
---|---|
CN114308120B (en) | 2024-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114308120A (en) | Phosphorus salt amphiphilic dual-functional organic catalyst and preparation method and application thereof | |
CN110938087B (en) | Organic metal-free catalyst with electrophilic nucleophilic bifunctional function, preparation method and application thereof | |
CN112390819B (en) | Organic catalyst, preparation method and application | |
Eßwein et al. | Anionic polymerization of oxirane in the presence of the polyiminophosphazene base t‐Bu‐P4 | |
CN101665567B (en) | Method for controllable ring-opening polymerization of cyclic compound catalyzed by carbene derivative | |
KR20160013874A (en) | Method and catalyst system for preparing polymers and block copolymers | |
CN101665565A (en) | Method for preparing polylactic acid by catalysis of carbene derivative | |
CN104817691A (en) | Polyene ether compounds and preparation method thereof | |
CN113087882A (en) | Organic catalytic system with multiple boron centers and application | |
CN115073736B (en) | Catalytic method for controllable copolymerization of epoxy and isothiocyanate | |
CN112387307B (en) | Electrophilic nucleophilic bifunctional organic catalyst, preparation method and application | |
WO2024087581A1 (en) | Preparation method for cyclic poly(l-lactide) | |
CN113105611A (en) | Polymerization method for ring-opening alternating copolymerization of anhydride compound and epoxy compound | |
Agarwal et al. | Ring‐opening polymerization of ε‐caprolactone and δ‐valerolactone using new Sm (III) μ‐halo‐bis (trimethylsilyl) amido complexes | |
CN110003452A (en) | A kind of preparation method of carbon monoxide-olefin polymeric and polylactide | |
CN110003455A (en) | A kind of preparation method of carbon monoxide-olefin polymeric and polylactide | |
CN115710288A (en) | Phosphorus salt organic boron catalyst, preparation method and application thereof | |
CN112812230A (en) | Catalytic load polymer and preparation method and application thereof | |
CN106380478B (en) | A kind of preparation method of three metal centers schiff bases aluminium compound, preparation method, application and polylactic acid | |
CN105399760B (en) | A kind of rare earth metal complex, carbon monoxide-olefin polymeric and application | |
KR101864005B1 (en) | Catalyst for polymerization of monomer having a ring-type ester group, and method of forming polymer using the catalyst | |
JPS6335659B2 (en) | ||
KR101210976B1 (en) | Organometallic Catalysts for the Preparation of Polylactide Resin, Preparation Method Thereof, and Polylactide Resin Prepared Therefrom | |
JP2004315588A (en) | Catalyst for ring-opening polymerization of heterocyclic compound | |
Hermanová et al. | Novel triazole-based aluminum complex for ring-opening polymerization of lactones |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant |