CN114479022B - Organoboron nonmetallic catalyst for polymerization and preparation method and application thereof - Google Patents
Organoboron nonmetallic catalyst for polymerization and preparation method and application thereof Download PDFInfo
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- CN114479022B CN114479022B CN202210043540.2A CN202210043540A CN114479022B CN 114479022 B CN114479022 B CN 114479022B CN 202210043540 A CN202210043540 A CN 202210043540A CN 114479022 B CN114479022 B CN 114479022B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 165
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002861 polymer material Substances 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 180
- 229920000642 polymer Polymers 0.000 claims description 101
- 239000001569 carbon dioxide Substances 0.000 claims description 90
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 90
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- 125000002947 alkylene group Chemical group 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 238000007334 copolymerization reaction Methods 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 51
- 239000012295 chemical reaction liquid Substances 0.000 claims description 49
- 239000002994 raw material Substances 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- -1 Aromatic radicals Chemical class 0.000 claims description 28
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 24
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 16
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 15
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 229920000515 polycarbonate Polymers 0.000 claims description 13
- 239000004417 polycarbonate Substances 0.000 claims description 13
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 12
- 150000003852 triazoles Chemical class 0.000 claims description 12
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 11
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 10
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 10
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 claims description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 claims description 10
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 229910010277 boron hydride Inorganic materials 0.000 claims description 9
- 125000004437 phosphorous atom Chemical group 0.000 claims description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 claims description 8
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 5
- 229930024421 Adenine Natural products 0.000 claims description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- 229960000643 adenine Drugs 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229940104302 cytosine Drugs 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 238000006197 hydroboration reaction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229940113082 thymine Drugs 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 229940035893 uracil Drugs 0.000 claims description 5
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical class O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Chemical class 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- BWCDLEQTELFBAW-UHFFFAOYSA-N 3h-dioxazole Chemical compound N1OOC=C1 BWCDLEQTELFBAW-UHFFFAOYSA-N 0.000 claims description 3
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003863 metallic catalyst Substances 0.000 claims 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 2
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical compound SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 claims 1
- 229920000180 alkyd Polymers 0.000 claims 1
- 150000004870 dithiazoles Chemical class 0.000 claims 1
- 150000003854 isothiazoles Chemical class 0.000 claims 1
- 150000002545 isoxazoles Chemical class 0.000 claims 1
- 150000004866 oxadiazoles Chemical class 0.000 claims 1
- 150000002916 oxazoles Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 114
- 238000005227 gel permeation chromatography Methods 0.000 description 88
- 239000012299 nitrogen atmosphere Substances 0.000 description 56
- 239000000047 product Substances 0.000 description 51
- 230000005311 nuclear magnetism Effects 0.000 description 48
- 238000001035 drying Methods 0.000 description 43
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000001376 precipitating effect Effects 0.000 description 36
- 239000002904 solvent Substances 0.000 description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 15
- 239000012986 chain transfer agent Substances 0.000 description 10
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 10
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000012442 inert solvent Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 125000004450 alkenylene group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920006237 degradable polymer Polymers 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
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- 238000012662 bulk polymerization Methods 0.000 description 3
- 125000005549 heteroarylene group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 3
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 2
- ZLUFYQVHJAVDHU-IHWYPQMZSA-N (6z)-2-methyl-2,3-dihydro-1,4-dioxocine-5,8-dione Chemical compound CC1COC(=O)\C=C/C(=O)O1 ZLUFYQVHJAVDHU-IHWYPQMZSA-N 0.000 description 2
- WZFLIWQTWXNLBC-UHFFFAOYSA-N C(CCC(=O)O)(=O)O.C1=CCCCC1 Chemical compound C(CCC(=O)O)(=O)O.C1=CCCCC1 WZFLIWQTWXNLBC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 239000003999 initiator Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CDHYSFKPWCVXHZ-UHFFFAOYSA-N 1,2,5-trimethylpiperazine Chemical compound CC1CN(C)C(C)CN1 CDHYSFKPWCVXHZ-UHFFFAOYSA-N 0.000 description 1
- DKYBVKMIZODYKL-UHFFFAOYSA-N 1,3-diazinane Chemical compound C1CNCNC1 DKYBVKMIZODYKL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229940037201 oris Drugs 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2672—Nitrogen or compounds thereof
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
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- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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Abstract
The invention discloses an organoboron nonmetallic catalyst for polymerization, which is shown in a formula (1), (2), (3) or (4), and discloses a preparation method and application thereof in preparing a high polymer material. The organoboron nonmetallic catalyst for polymerization provided by the invention has the advantages of simple preparation, high activity, convenient use, low cost and wide applicability, and is very suitable for industrial production. And the product is halogen-free, and the preparation and the use are more environment-friendly.
Description
Technical Field
The invention relates to the field of catalyst synthesis, in particular to a preparation method and application of a series of organoboron nonmetallic catalysts for polymerization.
Background
The polymer material has wide application in daily life of people, but most of non-degradable materials bring great convenience and cause great environmental pollution. With the development of synthetic chemistry, development of efficient and highly active catalytic systems for degradable high molecular materials (such as polyesters, polycarbonates, polyamides, polyurethanes, polyethers, etc.) has been attracting attention.
The university of major company research team topic group uses a chiral asymmetric Schiff base-metal complex catalytic system to catalyze the ring-opening copolymerization of single chiral alkylene oxide and carbon dioxide with high selectivity to form a crystallizable carbon dioxide-based polycarbonate material [ CN 102229745A ] with a highly isotactic structure; CN 102786677A; j.am.chem.soc.2012,134,5682-5688; macromolecules,2013,46,2128-2133]. The research group of Kaneler university catalyzes the ring-opening polymerization of propylene oxide by a bi-component catalytic system consisting of a binuclear metal Schiff base complex and bis (triphenyl phosphorane) imine to obtain an ultraviolet-degradable polypropylene oxide material with mechanical properties comparable to nylon-66 [ WO 2012/166889 A2; US 2014/0179895 Al; WO 2016/077455 Al; US 2017/0335061 Al; J.am.chem.Soc.2020,142,6800-6806]. The aliphatic polycarbonate block polymer is prepared by Zhejiang university research and development team, the functional nano material is prepared by utilizing the characteristic of microphase separation of the block polymer, and the functional nano material is expanded to an integrated circuit [ CN 108409954A; nano Letters,2017,17,1233-1239; macromolecules 2018,51,791-800 include applications in the fields of photoresists [ CN 107991842A ].
Although the various metal organic catalysts described above can prepare various degradable polymers with high efficiency and high selectivity, the catalysts often require complicated synthesis steps and severe synthesis conditions; in addition, the metal organic catalyst, especially some high-toxicity and high-dyeing catalyst, needs to be removed in the later polymerization stage, and once the catalyst remains unremoved, the problems of material discoloration, degradation and the like can be caused, and even the problems of harm to human bodies and the environment can be caused. This inevitably increases the process cost and limits the application of such polymeric materials in packaging, biomedical and microelectronics fields. Therefore, developing an efficient, highly selective, economical and environmentally friendly catalytic system is a great challenge in the field of degradable polymeric materials.
The outermost layer of the boron atom has 3 electrons and very good electrophilicity, so that the organoborane group is introduced into a catalytic system of the degradable polymer to play a role in activating the epoxy monomer and stabilizing the chain end. In 2016, research and development team of the university of Aphollander King science and technology reported that alternating copolymerization of cyclohexene oxide and carbon dioxide was achieved using organoboron reagent as catalyst and bis (triphenylphosphorane) imine chloride as initiator [ CN 107849233A; US 2018/011884 A1; J.am.chem.Soc.2016,138,11117-11120]. It was found that triethylboron acts to activate alkylene oxide and stabilize the polymer chain ends during catalysis. The research and development team of Zhejiang university uses triethylboron and analogues thereof and Lewis base to form Lewis acid-base pairs as catalytic initiator to initiate ring-opening polymerization or ring-opening copolymerization of alkylene oxide, and has very high catalytic activity [ CN 109705331A; WO 2020/135032 Al; macromolecules 2021,54, 2178-2186]. However, the flammability and thermal instability of triethylboron, and experimental errors resulting from batch weighing of two-component catalysts, limit the use of this system. The research shows that the organoboron and the quaternary ammonium salt are connected into the same system, and the metal-free organoboron catalyst with large-scale preparation, high heat resistance and unprecedented catalytic efficiency [ J.Am.chem.Soc.2020,142, 12245-12255 ] can be realized; am.chem.soc.,2021,143,3455-3465; CN2018111075279; PCT/CN2019/103919]. The catalyst is simple and efficient in synthesis, and the fixation rate of carbon dioxide and the product selectivity of the polymer reach more than 99%. Nevertheless, the presence of halogen groups in the quaternary ammonium or phosphonium salts on such catalysts is potentially detrimental to the use of the product.
In conclusion, the construction of a simple, efficient and high-selectivity halogen-free and nonmetal organic catalytic system realizes the efficient preparation of the degradable polymer and has good application prospect.
Disclosure of Invention
The invention aims to provide a halogen-free organoboron nonmetallic catalyst for polymerization, which shows excellent reactivity when applied to the preparation of degradable polymers.
The technical scheme provided by the invention is as follows:
an organoboron nonmetallic catalyst for polymerization, wherein the catalyst structure is provided with an electrophilic boric acid center and a nucleophilic tertiary amine or tertiary phosphorus center; the chemical formula of the organoboron nonmetallic catalyst for polymerization is shown as formula (1), (2), (3) or (4):
in the formulas (1) to (4), A 1 Or A 2 Each independently selected from nitrogen (N) or phosphorus (P) atoms;
in the formulae (1) to (4), R B Represents boron-containing substituent-BG 1 G 2 I=1 or 2, i represents a boron-containing substituent-BG 1 G 2 Is the number of (3);
in the formula (1) and the formula (4), R B ' represents boron-containing substituent-BG 3 G 4 J=1 or 2, j represents a boron-containing substituent-BG 3 G 4 Is the number of (3); i and j may be the same or different.
G 1 、G 2 、G 3 、G 4 Each independently is an unsubstituted or substituted group of: c (C) 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 3 -C 30 Alkenyl, C 3 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl, C 5 -C 30 One or more of the heteroaryl groups, or the group containing one or more of the O, S, N, si, P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, heteroaromatic groups having 5 to 20 carbon atoms; therein, B, G 1 And G 2 Or B, G 3 And G 4 May be linked to form a ring to form an aryl or cycloalkyl group;
G 1 、G 2 、G 3 、G 4 may be the same substituent or may represent different substituents, R B And R is B ' may be the same boron substituent or may be different boron substituentsPreferably R B And R is B ' are the same substituents.
In the formulae (1), (2) and (4), each K 1 、K 2 、K 7 Independently selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Alkenylene, C 6 -C 30 Arylene radicals, C 3 -C 30 Heterocyclylene, C 5 -C 30 One or more of the heteroarylene groups, or the group containing one or more of the O, S, N, si, P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; preferably C 1 -C 30 Alkylene of (C) is more preferred 1 -C 8 An alkylene group of (a);
in the formulas (1) and (2), K 3 0 or a group selected from the following unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Alkenylene, C 6 -C 30 Arylene radicals, C 3 -C 30 Heterocyclylene, C 5 -C 30 One or more of the heteroarylene groups, or the group containing one or more of the O, S, N, si, P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; preferably 0 or C 1 -C 30 Alkylene of (C) is more preferred 1 -C 8 An alkylene group of (a);
K 3 when 0, represents R A2 And A 1 Directly connected, where R A2 Is A-containing 2 Heterocyclic substituents of (a);
K 3 when the R is not 0, R A2 Is A-containing 2 substituent-A of (2) 2 R 2 R 3 Or contain A 2 Heterocyclic substituents of (a);
in the formulas (1) to (4), R is each 1 ～R 8 Independently selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 3 -C 30 Alkenyl, C 3 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl, C 5 -C 30 One or more of the heteroaryl groups, or the group containing one or more of the O, S, N, si, P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms;
Further, in formula (2), R 1 Preferably C 1 -C 30 Alkyl, C of (2) 3 -C 8 Cycloalkyl or C 6 -C 10 Aromatic groups, more preferably C 1 -C 8 Alkyl of (a);
in the formula (1) and the formula (2), R A2 Is A-containing 2 substituent-A of (2) 2 R 2 R 3 When, -A 2 R 2 R 3 R in (a) 2 、R 3 Preferably C 1 -C 15 Alkyl or C 3 -C 8 Cycloalkyl groups, more preferably C 1 -C 8 An alkyl group;
R A2 is A-containing 2 When the heterocyclic substituent of (C) is a, the compound contains A 2 Preferably pyrrole, pyridine, imidazole, thiazole, pyrazine, pyridazine, indole, pyrimidine, purine, morpholine, triazole, piperidine, piperazine, carbazole, quinoline, isoquinoline, benzimidazole, benzotriazole, adenine, uracil, cytosine, thymine, acridine, triazine, pyrrolidine, thiadiazole, pteridine, phenanthroline, isothiazole, dithiazole, oxazoleA derivative substituent of a group selected from the group consisting of a dioxazole, an isoxazole, an oxadiazole, and an oxazolidinone; more preferably pyridine, pyrimidine, piperazine, piperidine, N-methylpiperidine or 1,5, 7-triazabicyclo [4, 0]Sunflower-5-ene (TBD).
Or in the formula (1) and the formula (2), -K 3 -R A2 As shown in (5)
In the formula (5), K 3 ' C 1 -C 30 Alkylene groups of (C) are preferred 1 -C 8 An alkylene group of (a); a is that 2 、A 2 ' each independently is N or P, R 2 ’、R 3 ' each independently is C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 6 -C 30 One or more of the aromatic groups, preferably C 1 -C 8 An alkyl group;
or in formula (2), R 1 、A 1 、K 3 、R A2 Can be linked to form a ring containing A 1 And A 2 Heterocyclic substituents of (a); the A-containing 1 And A 2 Preferably imidazole, pyridazine, pyrimidine, piperazine, purine, pyrazole, pyrazine, triazole, triazine, thiadiazole, oxadiazole or pteridine, or a corresponding derivative substituent of the above; more preferred are imidazole, piperazine, triazole, 2,4, 5-trimethylpiperazine or heterocyclic compounds containing nitrogen and phosphine atoms.
In the formula (3), K 4 Is C 1 -C 30 Alkylene groups of (C) are more preferred 1 -C 8 An alkylene group of (a);
in the formula (3), K 5 、K 6 Each independently is 0 or selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Alkenylene, C 6 -C 30 Arylene radicals, C 3 -C 30 Heterocyclylene, C 5 -C 30 One or more of the heteroaromatic groups, orIs said group containing one or more of O, S, N, si, P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; preferably 0 or C 1 -C 30 Alkylene of (C) is more preferred 1 -C 8 An alkylene group of (a);
K 5 or K 6 Each 0 represents-A 1 R 4 R 5 、-A 2 R 6 R 7 Direct sum K 4 Connecting;
in the formula (3), R 4 ～R 7 Each independently preferably C 1 -C 30 Alkyl, C of (2) 3 -C 8 Cycloalkyl or C 6 -C 10 Aromatic groups, more preferably C 1 -C 8 Alkyl of (a);
in the formula (3), A 1 、R 4 、R 5 Or A 2 、R 6 、R 7 Can be respectively and independently connected into a ring to respectively form A-containing 1 Heterocyclic substituents or containing A 2 Heterocyclic substituents of (a); the A-containing 1 Heterocyclic substituents or containing A 2 Preferably pyrrole, pyridine, imidazole, thiazole, pyrazine, pyridazine, indole, pyrimidine, purine, morpholine, triazole, piperidine, piperazine, carbazole, quinoline, isoquinoline, benzimidazole, benzotriazole, adenine, uracil, cytosine, thymine, acridine, triazine, pyrrolidine, thiadiazole, pteridine, phenanthroline, isothiazole, dithiazole, oxazole, dioxazole, isoxazole, oxadiazole or oxazolidinone, or derivatives of the above; more preferably pyridine, imidazole, pyrimidine, piperazine, piperidine, N-methylpiperidine or triazole.
In the formula (3), or A 1 、K 5 、K 4 、K 6 、A 2 Can be linked to form a ring containing A 1 And A 2 Heterocyclic substituents of (a); the A-containing 1 And A 2 Preferably imidazole, pyridazine, pyrimidine, piperazine, purine, pyrazole, pyrazine, triazole, triazine, thiadiazole, oxadiazole or pteridine, or a corresponding derivative substituent of the above; more preferred is imidazole, pyrimidine, hexahydropyrimidine, triazine, 2, 4-dimethyl-6-ethyl hexahydropyrimidinyl or 2, 4-dimethyl-6 ethyl-2, 4, 6-triazinyl.
In the formula (4), R A1 Heterocyclic substituents which may be 0 or nitrogen-containing; preferably a triazole group;
in the formula (4), K 8 May be 0 or selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Alkenylene, C 6 -C 30 Arylene radicals, C 3 -C 30 Heterocyclylene, C 5 -C 30 One or more of the heteroarylene groups, or the group containing one or more of the O, S, N, si, P atoms; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; preferably 0 or C 1 -C 30 Alkylene of (C) is more preferred 1 -C 8 An alkylene group of (a);
R 8 preferably C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 6 -C 30 One or more of the aromatic groups; more preferably C 1 -C 8 An alkyl group.
In the formula (4), A 2 -R 8 Can be 0, i.e. K 7 And K 2 Directly connected, where R A1 And may not be 0.
Preferably, the G 1 、G 2 、G 3 、G 4 Each independently is an unsubstituted or substituted group of: c (C) 1 -C 15 Alkyl, C 3 -C 8 Cycloalkyl, C 3 -C 10 Alkenyl, C 6 -C 10 Aromatic radicals, C 3 -C 10 Silane group, C 6 -C 10 One or more of the phenolic oxy groups; the aryl group is preferably phenyl; the cycloalkyl group is preferably a cyclopentylalkyl group, a cyclohexenyl group, a pinenyl group or a pinenyl group; the substituent is preferably one or more selected from halogen atom, branched or straight chain alkyl group having 1 to 6 carbon atoms, branched or straight chain alkoxy group having 1 to 6 carbon atoms, branched or straight chain cycloalkyl group having 3 to 10 carbon atoms, aromatic group having 6 to 10 carbon atoms, heteroaromatic group having 5 to 10 carbon atoms;
Further, each G 1 、G 2 、G 3 、G 4 Each independently is preferably one of the following structures:
represented as a connecting bond;
each m is independently selected from any integer from 1 to 15.
Preferably, the-BG 1 G 2 、-BG 3 G 4 Each independently is represented as any one or more of the following:
each m is independently selected from any integer from 1 to 15.
Preferably, the organoboron nonmetallic catalyst for polymerization has one of the structures shown below:
the invention also provides a preparation method of the organoboron nonmetallic catalyst for polymerization, wherein the reaction formula is as follows:
each of which is provided withIndependently denoted as a carbon-carbon double bond or a carbon-carbon triple bond;
each i '=1 or 2, i' represents the number of hydrogen atoms on a terminal unsaturated alkene or alkyne; each j '=1 or 2, j' represents the number of hydrogen atoms on a terminal unsaturated alkene or alkyne; where i 'or j' =1, when,expressed as carbon-carbon triple bond, i 'or j' =2, < >>Represented as carbon-carbon double bonds, and i 'and j' may be equal or unequal.
The method comprises the following steps: carrying out hydroboration reaction on the reaction raw material containing unsaturated bonds and shown in the formula (6), the formula (7), the formula (8) or the formula (9) and the boron hydride compound shown in the formula (10) or the formula (11) to respectively prepare an organoboron nonmetallic catalyst for polymerization shown in the formula (1), the formula (2), the formula (3) or the formula (4); further, the specific operations of the method include: mixing the reaction raw materials containing unsaturated bonds and shown in the formula (6), the formula (7), the formula (8) or the formula (9) and the boron hydride compound shown in the formula (10) or the formula (11) in an organic solvent under the protection of inert gas, stirring for 1-500 hours (preferably 20-50 hours) at the temperature of-80-150 ℃ under the condition of room temperature, and carrying out hydroboration reaction, and after the reaction is finished, carrying out post-treatment on the reaction liquid to obtain the organoboron nonmetallic catalyst for polymerization. Alternatively, when R B And R is B ' being different substituents, it is desirable to use two different borohydrides of formula (10) and formula (11)When the raw materials of the materials are subjected to the hydroboration reaction according to the feeding sequence of the formula (10) and the formula (11), the specific operation is that the raw materials of the formula (6), the formula (7), the formula (8) or the formula (9) containing unsaturated bonds are firstly mixed with the boron hydride compound of the formula (10) under the protection of inert gas, the mixture is stirred for 1 to 500 hours (preferably for 20 to 50 hours) at the temperature of-80 to 150 ℃ under the protection of inert gas, then the boron hydride compound of the formula (11) is added under the protection of inert gas, the mixture is stirred for 1 to 500 hours (preferably for 20 to 50 hours) at the temperature of-80 to 150 ℃, and after the reaction is finished, the organic boron nonmetallic catalyst for polymerization is obtained by post-treatment of the reaction liquid.
The ratio of the unsaturated bond-containing reaction raw material represented by the formula (6), the formula (7), the formula (8) or the formula (9) to the amount of the boron hydride compound represented by the formula (10) or the formula (11) is 1:0.5 to 3, preferably 1:1.
Preferably, the organic solvent is selected from one or more of tetrahydrofuran, benzene, toluene, chloroform, hexane, diethyl ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1, 4-dioxane and pyridine; tetrahydrofuran is preferred.
The volume amount of the organic solvent is generally 1 to 10mL/mmol in terms of the amount of the unsaturated bond-containing reaction raw material represented by the formula (6), the formula (7), the formula (8) or the formula (9).
The post-treatment of the reaction liquid is generally to evaporate the solvent from the reaction liquid, wash the reaction liquid with hexane and prepare the organoboron nonmetallic catalyst for polymerization.
The inert gas is nitrogen.
It should be noted that the preparation method provided by the present invention is only one preparation method of the organic metal-free catalyst, and is not limited to the above reaction formula, and the reaction raw materials in the reaction formula include, but are not limited to, the formula (5), the formula (6), the formula (7) and the formula (8), and more preparation methods can be seen in specific examples.
The invention also provides application of the organoboron nonmetallic catalyst for polymerization in preparing high polymer materials.
Further, the application method comprises the following steps:
in the presence of organoboron nonmetallic catalyst for polymerization, one or more cyclic monomers undergo homopolymerization or copolymerization reaction, or one or more cyclic monomers undergo copolymerization reaction with one or more of carbon dioxide, carbon disulfide and carbon oxysulfide to obtain the high polymer material. Further, the reaction comprises: copolymerization of carbon dioxide and alkylene oxide to prepare aliphatic polycarbonate, ring-opening polymerization of alkylene oxide to prepare polyether, alkylene oxide and cyclic anhydride to prepare polyester, catalytic carbon oxysulfide and copolymerization of alkylene oxide to prepare polythiocarbonate. The polymer material with the required structure can be selectively obtained by regulating the structure and the dosage of the catalyst, adding different cyclic monomers and dosages and the dosage of carbon dioxide, carbon disulfide or carbon oxysulfide.
Further, the cyclic monomer is preferably of the following structure:
/>
when the organoboron nonmetallic catalyst for polymerization is applied to preparing high polymer materials, one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyalcohols and water can be added into the homo-polymerization or copolymerization reaction system to prepare corresponding polymer polyols as chain transfer agents.
The chain transfer agent is preferably of the structure:
as a preferred example of the present invention, when the organoboron nonmetallic catalyst for polymerization is applied to the preparation of high molecular materials, one or more polymers with alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups and carboxyl groups can be added into the homo-polymerization or copolymerization reaction system as macromolecular chain transfer agents to prepare corresponding block copolymers or graft copolymers.
The macromolecular chain transfer agent is selected from the following structures:
wherein,the main chain of the macromolecular chain transfer agent is represented by the number of the functional groups, which is not represented by the alcoholic hydroxyl group, the phenolic hydroxyl group, the amino group, the carboxyl group and the like, and may be any number from 1 to 50000 in theory.
The polymerization reaction with the addition of the chain transfer agent is generally carried out in an inert solvent such as chloroform, methylene chloride, toluene, tetrahydrofuran or alkylene oxide bulk, preferably toluene or alkylene oxide bulk as solvent; the polymerization temperature is generally maintained at-50 to 200 ℃, preferably 50 to 150 ℃; the pressure of the carbon dioxide is between 0.1 and 200MPa, preferably between 1 and 5MPa; the catalyst concentration can be in the range of 10 -6 ～10 -2 M is preferably at 10 -5 ～10 -3 M is used in; the ratio of chain transfer agent to reaction monomer is in the range of 10 -5 ～10 5 Preferably at 10 -3 ～10 3 Is used internally.
In the application of the organoboron nonmetallic catalyst for polymerization in preparing a high polymer material, the organoboron nonmetallic catalyst for polymerization can be loaded on an inorganic carrier or an organic carrier for use.
The application of the organoboron nonmetallic catalyst for polymerization in preparing high polymer materials comprises the following steps: catalyzing copolymerization of carbon dioxide and alkylene oxide to prepare aliphatic polycarbonate, catalyzing ring-opening polymerization of alkylene oxide to prepare polyether, catalyzing copolymerization of alkylene oxide and cyclic anhydride to prepare polyester, and catalyzing copolymerization of carbon oxysulfide and alkylene oxide to prepare polythiocarbonate. Adding chain transfer agent and catalyst into polymerization reaction for catalyzing copolymerization of carbon dioxide and alkylene oxide to prepare aliphatic polycarbonate, ring-opening polymerization of alkylene oxide to prepare polyether, copolymerization of alkylene oxide and cyclic anhydride to prepare polyester, copolymerization of carbon oxysulfide and alkylene oxide to prepare polythiocarbonate and other high molecular materials, regulating to required temperature, cooling after reacting for a certain time, precipitating, weighing to prepare corresponding polymer polyol, block copolymer or graft copolymer.
Aliphatic polycarbonate is prepared by catalyzing copolymerization of carbon dioxide and alkylene oxide: the polymerization is generally carried out in an inert solvent such as chloroform, methylene chloride, toluene, tetrahydrofuran or alkylene oxide bulk, preferably toluene or alkylene oxide bulk as solvent; and (3) dissolving a catalyst and one or more alkylene oxides in the inert solvent, regulating the temperature to a required temperature, filling the required carbon dioxide to prepare the polycarbonate efficiently, reacting for a certain time, cooling, precipitating and weighing to prepare the polycarbonate polymer material. Wherein: the polymerization temperature is generally maintained at-50 to 200 ℃, preferably 50 to 150 ℃; the pressure of the carbon dioxide is between 0.1 and 200 MPa, preferably between 1 and 5MPa; the catalyst concentration can be in the range of 10 -6 ～10 -2 M is preferably at 10 -5 ～10 -3 M is used in; the alkylene oxide monomer is as described above.
The molecular weight of the prepared polymer is 500-1500000Da, the polydispersity is 1.01-10.00, the selectivity ratio of the polycarbonate and the cyclic carbonate can be arbitrarily regulated and controlled between 1% and 100%, and the polyether content in the polycarbonate can be arbitrarily regulated and controlled between 0% and 99%.
Preparation of polyethers for the catalytic ring-opening polymerization of alkylene oxides: the polymerization is generally carried out in an inert solvent such as chloroform, methylene chloride, toluene, tetrahydrofuran or alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk as solvent; dissolving a catalyst in the above And in the solvent, regulating the temperature to the required temperature, reacting for a certain time, cooling, precipitating and weighing to prepare the polyether polymer material efficiently. Wherein: the polymerization temperature is generally maintained at-50 to 200 ℃, preferably 50 to 150 ℃; the catalyst concentration can be in the range of 10 -8 ～10 -2 M is preferably at 10 -5 ～10 -3 M is used in; the alkylene oxide monomers used are as described above.
Preparation of polyesters for catalytic alkylene oxides and cyclic anhydrides: the polymerization is generally carried out in an inert solvent such as chloroform, methylene chloride, toluene, tetrahydrofuran or alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk as solvent; and (3) dissolving the catalyst, the anhydride and the alkylene oxide in the solvent, regulating the temperature to a required temperature, reacting for a certain time, cooling, precipitating and weighing to prepare the polyether polymer material with high efficiency. Wherein: the polymerization temperature is generally maintained at-50 to 200 ℃, preferably 50 to 150 ℃; the catalyst concentration can be in the range of 10 -6 ～10 -2 M is preferably at 10 -5 ～10 -3 M is used in; the alkylene oxide monomers used are as described above; the cyclic anhydride monomer used is as described above.
Preparation of polythiocarbonate by catalyzing copolymerization of carbon oxysulfide and alkylene oxide: the polymerization is generally carried out in an inert solvent such as chloroform, methylene chloride, toluene, tetrahydrofuran or alkylene oxide bulk polymerization, preferably toluene or alkylene oxide bulk as solvent; dissolving catalyst and alkylene oxide in the solvent, regulating to required temperature, charging required carbon oxysulfide, reacting for a certain period of time, cooling, precipitating, and weighing to obtain the final product. Wherein: the polymerization temperature is generally maintained at-50 to 200 ℃, preferably 50 to 150 ℃; the pressure of the carbon dioxide is between 0.1MPa and 200MPa, preferably between 1 and 5MPa; the catalyst concentration can be in the range of 10 -6 ～10 -2 M is preferably at 10 -5 ～10 -3 M is used in; the alkylene oxide monomers used are as described above.
It should be noted that the addition of certain amounts of lewis base, lewis acid or other catalysts and cocatalysts, etc. during polymerization are also within the scope of this patent.
Compared with the existing metal-free organic polymerization catalyst system, the invention has the beneficial effects that: has the advantages of simple preparation, high activity, convenient use, low cost and wide applicability, and is very suitable for industrial production. And the product is halogen-free, and the preparation and the use are more environment-friendly.
Drawings
FIG. 1 is a catalyst B1 prepared in example 1 1 H NMR spectrum.
FIG. 2 is a schematic diagram of a polycyclohexenecarbonate prepared in application example 3 1 H NMR spectrum.
FIG. 3 is a GPC chart of the polycyclohexenyl carbonate prepared in application example 3.
Detailed Description
The following examples will better illustrate the invention, but it is emphasized that the invention is in no way limited to those described by the examples, but that several improvements and modifications can be made by one skilled in the art without departing from the principles of the invention, which fall within the scope of the appended claims.
Unless specifically indicated otherwise, the following terms used in the specification and claims have the following meanings:
alkyl refers to saturated aliphatic hydrocarbon groups, including straight and branched chain groups of 1 to 30 carbon atoms. Preferably a medium-sized alkyl group having 1 to 15 carbon atoms, more preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, and the like. More preferred are lower alkyl groups containing 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.
Cycloalkyl refers to an all-carbon monocyclic, fused ring or multicyclic fused ring group comprising 1 to 30 carbon atoms. Preferably a 3 to 8 membered all-carbon monocyclic, all-carbon 5-membered/6-membered or 6-membered/6-membered fused ring or polycyclic fused ring group, wherein one or more of the rings may contain one or more double bonds. More preferred are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexadienyl, adamantyl, cycloheptatrienyl and the like.
Alkenyl refers to unsaturated aliphatic hydrocarbon groups having a carbon-carbon double bond, including straight and branched chain groups of 1 to 30 carbon atoms. Preference is given to straight-chain and branched radicals having from 2 to 10 (further from 2 to 6) carbon atoms.
Alkynyl refers to unsaturated aliphatic hydrocarbon groups having a carbon-carbon triple bond, including straight and branched chain groups of 1 to 30 carbon atoms. Preference is given to straight-chain and branched radicals having from 2 to 10 (further from 2 to 6) carbon atoms.
Aryl refers to a group having at least one aromatic ring structure, preferably carbocyclic aromatic, heteroaromatic.
Heteroaryl refers to an aromatic group having 1 heteroatom as a ring forming atom, the remaining ring forming atoms being carbon, the ring structure meeting the shock rule, the heteroatoms including O, S, N, si, P atoms. Preferably a 5-, 6-or 7-membered ring. Further preferred heteroaromatic groups include, but are not limited to, furyl, thienyl, benzofuryl, benzothienyl, pyridyl, pyrrolyl, N-alkylpyrrolyl.
A heterocyclic group refers to a group that contains at least one heteroatom, including O, S, N, si, P atoms, in addition to carbon atoms, which form a ring. Preferably a 5-, 6-or 7-membered alicyclic heterocyclic ring, an aromatic heterocyclic ring.
Halogen means fluorine, chlorine, bromine or iodine.
Represented as a connecting key.
"__" refers to a bond between groups in a formula, a group attached to both sides, and "__" in a formula does not mean only one bond, but also multiple bonds to several atoms on one side.
"each" means each. For example "R' s 1 ～R 3 Independently selected from ", in particular R 1 、R 2 And R is 3 When the structural formula contains a plurality of R 1 When also referring to each R 1 Are independently represented by the respective structures, and may be the sameOr may be different.
The invention is described in detail below by way of specific examples:
example 1: synthesis of catalyst B1
In a glove box nitrogen atmosphere, adding 0.1mol of raw materials r1-1 and r1-2 into 100ml of tetrahydrofuran, reacting for 24 hours at room temperature, pumping out the solvent, washing with hexane to obtain a target product B1, wherein the yield is 95%, and the catalyst B1 1 The H NMR chart is shown in FIG. 1.
Example 2: synthesis of catalyst B2
In a nitrogen atmosphere of a glove box, 0.1mol of each of the raw materials r2-1 and r2-2 is added into 100ml of tetrahydrofuran, stirred for 24 hours at room temperature, the solvent is pumped out, and the solvent is washed with hexane, so that the target product B2 is obtained with the yield of 91%.
Example 3: synthesis of catalyst B3
In a nitrogen atmosphere of a glove box, 0.1mol of raw material r3-1 and 0.1mol of raw material r3-2 are added into 100ml of tetrahydrofuran, stirred for 24 hours at room temperature, the solvent is pumped out, and the mixture is washed with hexane, so that a target product B3 is obtained, and the yield is 93%.
Example 4: synthesis of catalyst B4
In a nitrogen atmosphere of a glove box, 0.2mol of raw material r4-1 and 0.1mol of raw material r4-2 are added into 100ml of tetrahydrofuran, stirred for 24 hours at room temperature, the solvent is pumped out, and the solvent is washed with hexane, so that a target product B4 can be obtained, and the yield is 99%.
Example 5: synthesis of catalyst B5
In a nitrogen atmosphere of a glove box, 0.3mol of raw material r5-1 and 0.1mol of raw material r5-2 are added into 100ml of tetrahydrofuran, stirred at room temperature for 48 hours, the solvent is pumped out, and the mixture is washed with hexane, so that a target product B5 can be obtained, and the yield is 95%.
Example 6: synthesis of catalyst B6
In a nitrogen atmosphere of a glove box, 0.3mol of raw material r6-1 and 0.1mol of raw material r6-2 are added into 100ml of tetrahydrofuran, stirred at room temperature for 48 hours, the solvent is pumped out, and the solvent is washed with hexane, so that a target product B6 is obtained, and the yield is 97%.
Example 7: synthesis of catalyst B7
In a nitrogen atmosphere of a glove box, 0.4mol of raw material r7-1 and 0.1mol of raw material r7-2 are added into 100ml of tetrahydrofuran, stirred at room temperature for 48 hours, the solvent is pumped out, and the mixture is washed with hexane, so that a target product B7 is obtained, and the yield is 93%.
Example 8: synthesis of catalyst B8
In a nitrogen atmosphere of a glove box, 0.2mol of raw material r8-1 and 0.1mol of raw material r8-2 are added into 100ml of tetrahydrofuran, stirred at room temperature for 48 hours, the solvent is pumped out, and the solvent is washed with hexane, so that a target product B8 can be obtained, and the yield is 95%.
Example 9: synthesis of catalyst B9
In a nitrogen atmosphere of a glove box, 0.2mol of raw material r9-1 and 0.1mol of raw material r9-2 are added into 100ml of tetrahydrofuran, stirred at room temperature for 48 hours, the solvent is pumped out, and the solvent is washed with hexane, so that a target product B9 is obtained, and the yield is 90%.
Example 10: synthesis of catalyst B10
(1) In a nitrogen atmosphere of a glove box, adding 0.1mol of raw material r10-1 and 0.1mol of raw material r10-2 into 100ml of diethyl ether, and reacting for 6 hours at room temperature to obtain r10-3;
(2) 0.1mol of r10-4 is added into the reaction liquid, the reaction is carried out for 8 hours at room temperature, the solvent is pumped out, and the target product B10 can be obtained after washing with hexane, and the yield is 90%.
Example 11: synthesis of catalyst B11
(1) In a nitrogen atmosphere of a glove box, adding 0.1mol of raw material r11-1 and 0.1mol of raw material r11-2 into 100ml of diethyl ether, and reacting for 6 hours at room temperature to obtain r11-3;
(2) Adding 0.1mol of r11-4 into the reaction liquid, and reacting for 8 hours at room temperature to obtain r11-5;
(3) 0.1mol of r11-6 is added into the reaction liquid to react for 24 hours at 80 ℃, the solvent is pumped out, and the target product B11 is obtained after washing with hexane, and the yield is 85%.
Example 12: synthesis of catalyst B12
(1) In a nitrogen atmosphere of a glove box, adding 0.1mol of raw material r12-1 and 0.1mol of raw material r12-2 into 100ml of diethyl ether, and reacting for 6 hours at room temperature to obtain r12-3;
(2) Adding 0.1mol of r12-4 into the reaction liquid, and reacting for 8 hours at room temperature to obtain r12-5;
(3) 0.1mol of r12-6 is added into the reaction liquid to react for 24 hours at 80 ℃, the solvent is pumped out, and the target product B12 is obtained after washing with hexane, and the yield is 87%.
Application example 1: under normal pressure, the catalyst B1 is used for catalyzing the ring-opening polymerization of the cyclohexene oxide (CHO)
Catalyst B1 (0.01 mmol) prepared in example 1 was taken in an autoclave and cyclohexene oxide (0.01 mol) was added and reacted at 80℃for 2h under nitrogen atmosphere in a glove box. And taking the reaction liquid to measure nuclear magnetism so as to characterize the conversion rate of the monomer. The polymer was precipitated from ethanol and, after drying, the polymer was characterized by GPC. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 2: under the pressurized condition, the catalyst B1 is used for catalyzing CHO ring-opening polymerization
Catalyst B1 (0.01 mmol) prepared in example 1 was taken in an autoclave and cyclohexane oxide (0.01 mol) was added and 2.0MPa CO was charged under nitrogen atmosphere in a glove box 2 And reacted at 80℃for 2 hours. And taking the reaction liquid to measure nuclear magnetism so as to characterize the conversion rate of the monomer. The polymer was precipitated from ethanol and, after drying, the polymer was characterized by GPC. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 3: catalyzing CHO and carbon dioxide copolymerization with catalyst B1
In a glove box nitrogen atmosphereIn the middle, catalyst B1 (0.01 mmol) prepared in example 1 was charged into an autoclave, and cyclohexene oxide (0.01 mol) was charged with 2.0MPa of CO 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, wherein a nuclear magnetism spectrogram is shown in figure 2. The polymer was precipitated from ethanol and, after drying, the polymer was characterized by GPC. The results of the characterization of nuclear magnetism and GPC are shown in Table 1. GPC patterns of the obtained polymer are shown in FIG. 3.
Application example 4: preparation of polyepoxy cyclohexane-polycyclohexene carbonate block polymer by catalyzing CHO and carbon dioxide to copolymerize by catalyst B1
Catalyst B1 (0.01 mmol) prepared in example 1 was taken in an autoclave and cyclohexane oxide (0.01 mol) was added and CO 2.0MPa was charged in a glove box under nitrogen atmosphere 2 The reaction is carried out for 30min at 80 ℃ and then for 1.5h at 150 ℃. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product. The polymer was precipitated from ethanol and, after drying, the polymer was characterized by GPC. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 5: catalyzing CHO and carbon dioxide copolymerization with catalyst B2
Catalyst B2 (0.01 mmol) prepared in example 2 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 6: catalyzing CHO and carbon dioxide copolymerization with catalyst B3
Catalyst B3 (0.01 mmol) prepared in example 3 was taken into an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove boxCharging CO of 2.0MPa 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 7: catalyzing CHO and carbon dioxide copolymerization with catalyst B4
Catalyst B4 (0.01 mmol) prepared in example 4 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 8: catalyzing CHO and carbon dioxide copolymerization with catalyst B5
Catalyst B5 (0.01 mmol) prepared in example 5 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 9: catalyzing CHO and carbon dioxide copolymerization with catalyst B6
Catalyst B6 (0.01 mmol) prepared in example 6 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 10: catalyzing CHO and carbon dioxide copolymerization with catalyst B7
Catalyst B7 (0.01 mmol) prepared in example 7 was taken in an autoclave and CHO (0.01 mol) was charged to 2.0MPa under nitrogen atmosphere in a glove boxCO of (c) 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 11: catalyzing CHO and carbon dioxide copolymerization with catalyst B8
Catalyst B8 (0.01 mmol) prepared in example 8 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 12: catalyzing CHO and carbon dioxide copolymerization with catalyst B9
Catalyst B9 (0.01 mmol) prepared in example 9 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 13: catalyzing CHO and carbon dioxide copolymerization with catalyst B10
Catalyst B10 (0.01 mmol) prepared in example 10 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 14: catalyzing CHO and carbon dioxide copolymerization with catalyst B11
Catalyst B11 (0.01 mmol) prepared in example 11 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 15: catalyzing CHO and carbon dioxide copolymerization with catalyst B12
Catalyst B12 (0.01 mmol) prepared in example 12 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the monomer conversion rate and the selectivity of a product, precipitating the polymer from ethanol, and carrying out GPC (GPC) representation on the polymer after drying. The results are shown in Table 1.
Application example 16: catalyzing CHO and carbon dioxide copolymerization with catalyst B2
Catalyst B2 (0.1 mmol) prepared in example 2 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 17: catalyzing CHO and carbon dioxide copolymerization with catalyst B2
Catalyst B2 (0.1 mmol) prepared in example 2 was taken in an autoclave and CHO (0.05 mol) was charged with CO at 2.0MPa under nitrogen atmosphere in a glove box 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 18: catalyzing CHO and carbon dioxide copolymerization with catalyst B2
Catalyst B2 (0.01 mmol) prepared in example 2 was taken in an autoclave and CHO (0.05 mol) was charged in a glove box under nitrogen atmosphere with 2.0CO of MPa 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 19: catalyzing CHO and carbon dioxide copolymerization with catalyst B2
Catalyst B2 (0.01 mmol) prepared in example 2 was taken in an autoclave and CHO (0.1 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 8 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 20: catalyzing CHO and carbon dioxide copolymerization with catalyst B2
Catalyst B2 (0.01 mmol) prepared in example 2 was taken in an autoclave and CHO (0.5 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 16h. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 21: catalyzing PO and carbon dioxide copolymerization with catalyst B3
Catalyst B3 (0.01 mmol) prepared in example 3 was taken in an autoclave and PO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO at 2.0MPa was charged 2 And reacted at 0℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 22: catalyzing PO and carbon dioxide copolymerization with catalyst B3
Catalyst B3 (0.01 mmol) prepared in example 3 was taken into an autoclave under nitrogen atmosphere in a glove box Adding PO (0.01 mol) and charging CO of 2.0MPa 2 And reacted at 25℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 23: catalyzing PO and carbon dioxide copolymerization with catalyst B3
Catalyst B3 (0.01 mmol) prepared in example 3 was taken in an autoclave and PO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO at 2.0MPa was charged 2 And reacted at 60℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 24: catalyzing PO and carbon dioxide copolymerization with catalyst B3
Catalyst B3 (0.01 mmol) prepared in example 3 was taken in an autoclave and PO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO at 2.0MPa was charged 2 And reacted at 80℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 25: catalyzing PO and carbon dioxide copolymerization with catalyst B3
Catalyst B3 (0.01 mmol) prepared in example 3 was taken in an autoclave and PO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO at 2.0MPa was charged 2 And reacted at 120℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. See table 1.
Application example 26: catalyzing CHO and carbon dioxide copolymerization with catalyst B4
Catalyst B4 (0.01 mmol) prepared in example 4 was taken under nitrogen in a glove box and added to high pressureAdding CHO (0.01 mol) into a kettle, and charging CO of 2.0MPa 2 And reacted at 150℃for 0.5h. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. See table 1.
Application example 27: catalyzing CHO and carbon dioxide copolymerization with catalyst B4
Catalyst B4 (0.01 mmol) prepared in example 4 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 1 hour. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 28: catalyzing CHO and carbon dioxide copolymerization with catalyst B4
Catalyst B4 (0.01 mmol) prepared in example 4 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO 2.0MPa was charged 2 And reacted at 150℃for 4 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results are shown in Table 1.
Application example 29: catalyzing CHO and carbon dioxide copolymerization with catalyst B5
Catalyst B5 (0.01 mmol) prepared in example 5 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box, 1 ml of Tetrahydrofuran (THF) was added and 2.0MPa of CO was added 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 30: catalyzing CHO and carbon dioxide copolymerization with catalyst B5
Nitrogen in glove boxIn an air atmosphere, the catalyst B5 (0.01 mmol) prepared in example 5 was taken and introduced into an autoclave, CHO (0.01 mol) was added, 1 ml toluene (Tol) was added and CO 2.0MPa was charged 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 31: catalyzing CHO and carbon dioxide copolymerization with catalyst B5
Catalyst B5 (0.01 mmol) prepared in example 5 was taken in an autoclave and CHO (0.01 mol) was added under nitrogen atmosphere in a glove box, 1 ml chloroform (CHCl) 3 ) CO charged to 2.0MPa 2 And reacted at 150℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, precipitating the polymer from ethanol, drying, and carrying out GPC (GPC) representation on the polymer. The results of the characterization of nuclear magnetism and GPC are shown in Table 1.
Application example 32: PO ring-opening polymerization catalyzed by catalyst B6
Catalyst B6 (0.01 mmol) prepared in example 6 was taken in an autoclave and PO (0.01 mol) was added without carbon dioxide addition and reacted at 80℃for 2h under nitrogen atmosphere in the glove box. And (3) measuring nuclear magnetism of the reaction liquid to represent the conversion rate of the monomer and the selectivity of the product, directly pumping out residual PO to obtain a polymer, and carrying out GPC (GPC) representation on the polymer after drying. The nuclear magnetism and GPC characterization results are shown in Table 1.
Application example 33: catalyzing PO and carbon dioxide copolymerization with catalyst B6
Catalyst B6 (0.01 mmol) prepared in example 6 was taken in an autoclave and PO (0.01 mol) was added and CO at 0.5MPa was charged in a glove box under nitrogen atmosphere 2 And reacted at 80℃for 2 hours. Then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism to characterize the monomerThe conversion and the selectivity of the product are directly pumped out to obtain the polymer, and GPC characterization is carried out on the polymer after drying. See table 1.
Application example 34: catalyzing PO and carbon dioxide copolymerization with catalyst B6
Catalyst B6 (0.01 mmol) prepared in example 6 was taken in an autoclave and PO (0.01 mol) was added under nitrogen atmosphere in a glove box and CO at 1.5MPa was charged 2 And reacted at 80℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, directly pumping out residual PO to obtain a polymer, and carrying out GPC (gel permeation chromatography) representation on the polymer after drying. See table 1.
Application example 35: catalyzing PO and carbon dioxide copolymerization with catalyst B6
Catalyst B6 (0.01 mmol) prepared in example 6 was taken in an autoclave and PO (0.01 mol) was added and charged with 3.0MPa CO in a glove box under nitrogen atmosphere 2 And reacted at 80℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, directly pumping out residual PO to obtain a polymer, and carrying out GPC (gel permeation chromatography) representation on the polymer after drying. See table 1.
Application example 36: catalytic copolymerization of Ethylene Oxide (EO) with carbon dioxide Using catalyst B1
Catalyst B1 (0.01 mmol) prepared in example 1 was taken in an autoclave and EO (0.01 mol) was added and CO at 2.0MPa was charged under nitrogen atmosphere in a glove box 2 And reacted at 60℃for 2 hours. And then releasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism so as to represent the conversion rate of the monomer and the selectivity of the product, directly pumping residual EO to obtain a polymer, and carrying out GPC (GPC) representation on the polymer after drying. See table 1.
Application example 37: copolymerization of 4-vinylcyclohexene oxide (VCHO) with carbon dioxide Using catalyst B1
Catalyst B1 (0.01 mmol) prepared in example 1 was taken in an autoclave and 4-vinylcyclohexene oxide (0.01 mol) was charged in a glove box under nitrogen atmosphere, 2.0MPa of CO 2 And reacted at 150℃for 2 hours. And thenReleasing carbon dioxide, taking the reaction liquid to measure nuclear magnetism to characterize the conversion rate of monomers and the selectivity of products, precipitating the polymer from ethanol, and performing GPC characterization on the polymer after drying. See table 1.
Table 1 shows the results of the polymerization products of application examples 1 to 37
1 M n Molecular weight data, as measured by gel permeation chromatography; 2 PDI: molecular weight distribution, as measured by gel permeation chromatography.
As can be seen from Table 1, the organoboron nonmetallic catalyst for polymerization shows good catalytic effect on the self-polymerization of various alkylene oxides and the copolymerization with carbon dioxide, has higher catalytic activity and monomer universality, and obtains polyether or polycarbonate polymers with narrow molecular weight distribution.
Application example 38: preparation of Polycyclohexene carbonate Using catalyst B7 and chain transfer agent
Catalyst B7 (0.02 mmol) prepared in example 7 was taken in an autoclave, cyclohexanediol (0.20 mmol) was added as chain transfer agent and cyclohexene oxide (0.02 mol) was added under nitrogen atmosphere in a glove box, and 1.5MPa of CO was charged 2 And reacted at 80℃for 24 hours. The carbon dioxide was then released, the polymer was precipitated in ethanol and, after drying, the polymer was subjected to nuclear magnetic resonance and Gel Permeation Chromatography (GPC) characterization, with a number average molecular weight of 11.5kg/mol and a polydispersity of 1.02.
Application example 39: preparation of Polycyclohexene carbonate-Polypropylene glycol Block copolymer Using catalyst B7 and Polypropylene glycol as macromolecular chain transfer agent
Catalyst B7 (0.02 mmol) prepared in example 7 was taken in an autoclave, polypropylene glycol (0.20 mmol) was added as a macromolecular chain transfer agent and cyclohexene oxide (0.02 mol) was added under nitrogen atmosphere in a glove box, and CO at 1.5MPa was charged 2 And reacted at 80℃for 24 hours. Carbon dioxide is then released, the polymer is precipitated in ethanol, and the polymer is subjected to nuclear magnetic resonance and Gel Permeation Chromatography (GPC) characterization after drying.
Application example 40: preparation of cyclohexene succinate by using catalyst B10
Catalyst B10 (0.01 mmol) prepared in example 10 was taken in a pressure-resistant bottle, epoxycyclohexane (0.01 mol) was added, succinic anhydride (0.01 mol) was added, and reacted at 60℃for 24 hours under a nitrogen atmosphere in a glove box. And (3) precipitating the polymer in petroleum ether, and drying to obtain the cyclohexene succinate.
Application example 41: preparation of Poly (propylene maleate) Using catalyst B10
Catalyst B10 (10.01 mmol) prepared in example 10 was taken in a pressure-resistant bottle under a nitrogen atmosphere in a glove box, propylene oxide (0.01 mol) was added, maleic anhydride (0.01 mol) was added, and the reaction was carried out at 60℃for 24 hours. The polymer is precipitated in petroleum ether and dried to obtain the poly (propylene maleate).
Application example 42: preparation of Polycyclohexene carbonate-Polycyclohexene succinate Block copolymer Using catalyst B10
Catalyst B10 (0.02 mmol) prepared in example 10 was taken in an autoclave and cyclohexene oxide (0.01 mol) and succinic acid (2 mmol) was added to CO charged at 0.8MPa in a glove box under nitrogen atmosphere 2 And reacted at 100℃for 12 hours. The carbon dioxide was then released, the polymer was precipitated in ethanol and, after drying, the polymer was subjected to nuclear magnetic resonance and Gel Permeation Chromatography (GPC) characterization, with a number average molecular weight of 15.6kg/mol and a polydispersity of 1.19.
Application example 43: preparation of monothiopolycyclohexenecarbonate using catalyst B10
Catalyst B10 (0.02 mmol) prepared in example 10 was taken in an autoclave and cyclohexene oxide (0.01 mol) was added, carbon Oxysulfide (COS) was charged at 1.0MPa, and reacted at 70℃for 2h under a nitrogen atmosphere in a glove box. And then releasing COS, precipitating the polymer in ethanol, and drying to obtain the monothio-polycyclohexenecarbonate.
Application example 44: preparation of polylactide Using catalyst B12
Catalyst B12 (0.02 mmol) prepared in example 12 was taken in an autoclave and lactide (0.01 mol) was added, 5 ml of chloroform was added and reacted at 50℃for 2h under nitrogen atmosphere in a glove box. The polymer is precipitated in ethanol and dried to obtain the polylactide.
Application example 45: preparation of polyphosphates using catalyst B12
Catalyst B12 (0.02 mmol) prepared in example 12 was taken in an autoclave and phosphate (0.01 mol) was added, 5ml of chloroform was added and reacted at 50℃for 3h under nitrogen atmosphere in a glove box. The polymer is precipitated in ethanol and dried to obtain the polyphosphate.
Application example 46: preparation of polyphosphate-polypropylene carbonate Block copolymer Using catalyst B12
Catalyst B12 (0.01 mmol) prepared in example 12 was taken in an autoclave and propylene oxide (0.01 mol) was added under nitrogen atmosphere in a glove box and CO at 1.5MPa was charged 2 And reacted at 80℃for 2 hours. Then, carbon dioxide was released, and phosphate (0.01 mol) was sequentially added to the mixture in a nitrogen atmosphere in a glove box, and the mixture was reacted at 50℃for 3 hours. Taking the reaction liquid to measure nuclear magnetism to characterize the conversion rate of the monomer, precipitating the polymer from petroleum ether, and performing GPC characterization on the polymer after drying.
Claims (10)
1. An organoboron nonmetallic catalyst for polymerization, which is characterized in that the chemical formula of the organoboron nonmetallic catalyst for polymerization is shown as formula (1), (3) or (4):
in the formula (1), (3) or (4), A 1 Or A 2 Each independently selected from nitrogen or phosphorus atoms;
in the formula (1), (3) or (4), R B Represents boron-containing substituent-BG 1 G 2 I=1 or 2, i represents a boron-containing substituent-BG 1 G 2 Is the number of (3);
in the formula (1) and the formula (4), R B ' represents boron-containing substituent-BG 3 G 4 J=1 or 2, j represents a boron-containing substituent-BG 3 G 4 Is the number of (3); i and j may be the same or different;
the-BG 1 G 2 、-BG 3 G 4 Each independently represented as any one or more ofA method of:
each m is independently selected from any integer from 1 to 15;
in the formula (1) and the formula (4), each K is 1 、K 2 、K 7 Independently selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 A cycloalkylene group; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms;
in the formula (1), K 3 0 or a group selected from the following unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 A cycloalkylene group; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; k (K) 3 When 0, represents R A2 And A 1 Directly connected, where R A2 Is A-containing 2 Heterocyclic substituents of (a);
K 3 when the R is not 0, R A2 Is A-containing 2 substituent-A of (2) 2 R 2 R 3 Or contain A 2 Heterocyclic substituents of (a);
in the formula (1), (3) or (4), each R 2 ～R 8 Independently selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 3 -C 30 Alkenyl, C 3 -C 30 Alkynyl, C 6 -C 30 Aromatic radicals, C 3 -C 30 Heterocyclyl, C 5 -C 30 One or more of the heteroaromatic groups; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms;
or in formula (1), -K 3 -R A2 As shown in (5)
In the formula (5), K 3 ' C 1 -C 30 Alkylene group A of (A) 2 、A 2 ' each independently is N or P, R 2 ’、R 3 ' each independently is C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 6 -C 30 One or more of the aromatic groups;
in the formula (3), K 4 Is C 1 -C 30 Alkylene group, K 5 、K 6 Each independently is 0 or selected from the following groups, unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 A cycloalkylene group; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms; k (K) 5 Or K 6 Each 0 represents-A 1 R 4 R 5 、-A 2 R 6 R 7 Direct sum K 4 Connecting;
in the formula (3), A 1 、R 4 、R 5 Or A 2 、R 6 、R 7 Can be respectively and independently connected into a ring to respectively form A-containing 1 Heterocyclic substituents or containing A 2 Heterocyclic substituents of (a);
in the formula (3), or A 1 、K 5 、K 4 、K 6 、A 2 Are connected into a ring to form a containing A 1 And A 2 Heterocyclic substituents of (a);
in the formula (4), R A1 Is triazole;
in the formula (4), K 8 0 or a group selected from the following unsubstituted or substituted: c (C) 1 -C 30 Alkylene, C 3 -C 30 A cycloalkylene group; wherein the substituents are selected from one or more of halogen atoms, branched or straight chain alkyl groups having 1 to 20 carbon atoms, branched or straight chain alkoxy groups having 1 to 20 carbon atoms, branched or straight chain cycloalkyl groups having 3 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, heteroaromatic groups having 5 to 30 carbon atoms.
2. The organoboron nonmetallic catalyst for polymerization of claim 1, characterized in that in the formulas (1), (4), each K 1 、K 2 、K 7 Is C 1 -C 30 An alkylene group of (a);
in the formula (1), K 3 Is 0 or C 1 -C 30 An alkylene group of (a);
in the formula (1), R A2 Is A-containing 2 substituent-A of (2) 2 R 2 R 3 When, -A 2 R 2 R 3 R in (a) 2 、R 3 Is C 1 -C 15 Alkyl or C 3 -C 8 Cycloalkyl;
in the formula (1), R A2 In the case of a heterocyclic substituent containing A2, the heterocyclic substituent containing A 2 Heterocyclic substituents of (2) are pyrrole, pyridine, imidazole, thiazole, pyrazine, pyridazine, indole, pyrimidine, purine, morpholine, triazole, piperidine, piperazine, carbazole, quinoline, isoquinoline, benzimidazole, benzotriazole, adenine, uracil, cytosine, thymine, acridine, triazine, pyrrolidine, thiadiazole, pteridine, phenanthroline, quinoline, isoquinoline, benzimidazole, benzotriazol, adenine, uracil, cytosine, thymine, acridine, triazine, pyrrolidine, thiodiazole, pteridine, phenanthroline, quinoline, or mixtures thereof, Isothiazoles, dithiazoles, oxazoles, dioxazoles, isoxazoles, oxadiazoles or oxazolidinones, or derivatives of the above;
in the formula (3), K 4 Is C 1 -C 8 An alkylene group of (a);
in the formula (3), K 5 、K 6 Is 0 or C 1 -C 30 An alkylene group of (a);
in the formula (3), R 4 ～R 7 Each independently is C 1 -C 30 Alkyl, C of (2) 3 -C 8 Cycloalkyl or C 6 -C 10 An aromatic group;
in the formula (3), A 1 、R 4 、R 5 Or A 2 、R 6 、R 7 Each independently connected to form a ring, each of which contains A 1 Heterocyclic substituents or containing A 2 When the heterocyclic substituent of (C) is a, the compound contains A 1 Heterocyclic substituents or containing A 2 Heterocyclic substituents of (2) are pyrrole, pyridine, imidazole, thiazole, pyrazine, pyridazine, indole, pyrimidine, purine, morpholine, triazole, piperidine, piperazine, carbazole, quinoline, isoquinoline, benzimidazole, benzotriazole, adenine, uracil, cytosine, thymine, acridine, triazine, pyrrolidine, thiadiazole, pteridine, phenanthroline, isothiazole, dithiazole, oxazole, dioxazole, isoxazole, oxadiazole or oxazolidinone, or derivatives of the foregoing;
in the formula (3), A 1 、K 5 、K 4 、K 6 、A 2 Are connected into a ring to form a containing A 1 And A 2 When the heterocyclic substituent of (C) is a, the compound contains A 1 And A 2 Heterocyclic substituents of (2) are imidazole, pyridazine, pyrimidine, piperazine, purine, pyrazole, pyrazine, triazole, triazine, thiadiazole, oxadiazole or pteridine, or corresponding derivative substituents of the foregoing;
In the formula (4), R A1 Is a triazole group;
in the formula (4), K 8 Is 0 or C 1 -C 30 An alkylene group of (a);
in the formula (4), R 8 Is C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 6 -C 30 One or more of the aromatic groups.
3. The organoboron non-metallic catalyst for polymerization of claim 1, wherein said organoboron non-metallic catalyst for polymerization has one of the following structures:
4. the method for preparing an organoboron nonmetallic catalyst for polymerization according to claim 1, characterized in that the reaction formula of the method is as follows:
each of which is provided withIndependently denoted as a carbon-carbon double bond or a carbon-carbon triple bond;
each i '=1 or 2, i' represents the number of hydrogen atoms on a terminal unsaturated alkene or alkyne; each j '=1 or 2, j' represents the number of hydrogen atoms on a terminal unsaturated alkene or alkyne; where i 'or j' =1,expressed as carbon-carbon triple bond, i 'or j' =2, ">Represented as carbon-carbon double bonds, and i 'and j' may be equal or unequal;
in the formula (1), (3) or (4), R B Represents boron-containing substituent-BG 1 G 2 I=1 or 2, i represents a boron-containing substituent-BG 1 G 2 Is the number of (3);
in the formula (1) and the formula (4), R B ' represents boron-containing substituent-BG 3 G 4 J=1 or 2, j represents a boron-containing substituent-BG 3 G 4 Is the number of (3);
G 1 、G 2 、G 3 、G 4 is defined as in claim 1;
Each K is 1 ～K 8 Is defined as in claim 1;
R A2 、R A1 is defined as in claim 1;
each R is 2 ～R 8 Is defined as in claim 1;
the method comprises the following steps: the organoboron nonmetallic catalyst for polymerization represented by the formula (1), the formula (3) or the formula (4) is produced by subjecting a reaction raw material containing an unsaturated bond represented by the formula (6), the formula (8) or the formula (9) to a borohydride reaction represented by the formula (10) or the formula (11).
5. The method according to claim 4, characterized in that the specific operation of the method is: mixing a reaction raw material containing unsaturated bonds and shown in a formula (6), a formula (8) or a formula (9) in an organic solvent and a boron hydride compound shown in a formula (10) or a formula (11) under the protection of inert gas, stirring for 1-500 hours at the temperature of-80-150 ℃ to carry out hydroboration reaction, and after the reaction is finished, carrying out post-treatment on a reaction solution to obtain an organoboron nonmetallic catalyst for polymerization; when R is B And R is B When two different boron hydride materials of the formula (10) and the formula (11) are needed to be used as different substituents,' the boron hydrogenation reaction is carried out according to the feeding sequence of the formula (10) and the formula (11), specifically, the method comprises the steps of mixing the reaction raw material containing unsaturated bonds and shown in the formula (6), the formula (8) or the formula (9) with the boron hydride shown in the formula (10) under the protection of inert gas in an organic solvent, stirring for 1-500 hours at the temperature of-80-150 ℃ to carry out the boron hydrogenation reaction, and then adding the mixture into the mixture under the protection of inert gas (11) The boron hydride compound is stirred for 1 to 500 hours at the temperature of-80 to 150 ℃ to carry out the hydroboration reaction, and after the reaction is finished, the organic boron nonmetallic catalyst for polymerization is obtained by the post-treatment of the reaction liquid.
6. The use of the organoboron nonmetallic catalyst for polymerization in the preparation of a polymer material according to any one of claims 1-3, characterized in that the method of the use is that under the contact of the organoboron nonmetallic catalyst for polymerization, one or more cyclic monomers undergo homo-polymerization or copolymerization, or one or more cyclic monomers undergo copolymerization with one or more of carbon dioxide, carbon disulfide and carbon oxysulfide to obtain the polymer material.
7. Use of an organoboron non-metallic catalyst for polymerization according to claim 6 for the preparation of polymeric materials, characterized in that the reaction of said use comprises: copolymerization of carbon dioxide and alkylene oxide to prepare aliphatic polycarbonate, ring-opening polymerization of alkylene oxide to prepare polyether, alkylene oxide and cyclic anhydride to prepare polyester, catalytic carbon oxysulfide and copolymerization of alkylene oxide to prepare polythiocarbonate.
8. The use of an organoboron nonmetallic catalyst for polymerization according to claim 6 for preparing a polymer material, wherein one or more alcohol compounds, acid compounds, amine compounds, water as chain transfer agents can be added to the homo-or copolymerization reaction system to prepare the corresponding polymer polyol.
9. The use of an organoboron nonmetallic catalyst for polymerization according to claim 6 for preparing a polymer material, wherein one or more polyols, polycarboxylic acids as chain transfer agents can be added to the homo-or copolymerization reaction system to prepare the corresponding polymer polyol.
10. The use of an organoboron nonmetallic catalyst for polymerization according to claim 6 for preparing a polymer material, wherein one or more polyhydric alkyds can be added as chain transfer agents to the homo-or copolymerization reaction system to prepare the corresponding polymer polyol.
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| 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 |
| CN112390819A (en) * | 2019-08-19 | 2021-02-23 | 浙江大学 | Organic catalyst, preparation method and application |
| CN113087882A (en) * | 2020-01-08 | 2021-07-09 | 浙江大学 | Organic catalytic system with multiple boron centers and application |
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| 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 |
| CN112390819A (en) * | 2019-08-19 | 2021-02-23 | 浙江大学 | Organic catalyst, preparation method and application |
| CN113087882A (en) * | 2020-01-08 | 2021-07-09 | 浙江大学 | Organic catalytic system with multiple boron centers and application |
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