CN114805781A - Poly (carbonate-ether) polyol and preparation method thereof - Google Patents
Poly (carbonate-ether) polyol and preparation method thereof Download PDFInfo
- Publication number
- CN114805781A CN114805781A CN202210548812.4A CN202210548812A CN114805781A CN 114805781 A CN114805781 A CN 114805781A CN 202210548812 A CN202210548812 A CN 202210548812A CN 114805781 A CN114805781 A CN 114805781A
- Authority
- CN
- China
- Prior art keywords
- carbonate
- polyol
- ether
- zinc
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005862 polyol Polymers 0.000 title claims abstract description 73
- 150000003077 polyols Chemical class 0.000 title claims abstract description 73
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000004917 polyol method Methods 0.000 title description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910021654 trace metal Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- -1 cyclopentane epoxide Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001261 hydroxy acids Chemical class 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 2
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 claims description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical group C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 claims description 2
- HEQUOWMMDQTGCX-UHFFFAOYSA-L dicesium;oxalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C([O-])=O HEQUOWMMDQTGCX-UHFFFAOYSA-L 0.000 claims description 2
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 40
- 239000006227 byproduct Substances 0.000 abstract description 24
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 23
- 125000005587 carbonate group Chemical group 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 description 58
- 239000000047 product Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- 230000000694 effects Effects 0.000 description 26
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 239000002245 particle Substances 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 17
- 238000004448 titration Methods 0.000 description 17
- 238000005227 gel permeation chromatography Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 230000007547 defect Effects 0.000 description 11
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229960004337 hydroquinone Drugs 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HMDRRXODEPDLJT-UHFFFAOYSA-N [K].N#C[Ru](C#N)(C#N)(C#N)(C#N)C#N Chemical compound [K].N#C[Ru](C#N)(C#N)(C#N)(C#N)C#N HMDRRXODEPDLJT-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
- C08G65/26—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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses poly (carbonate-ether) polyol and a preparation method thereof, belonging to the technical field of polymer preparation. According to the preparation method, the bi-metal catalyst is designed and synthesized, and the bi-metal catalyst is used for catalyzing the epoxy compound and the chain transfer agent to perform polymerization reaction under the condition of carbon dioxide pressure to obtain the poly (carbonate-ether) polyol, so that the high-efficiency preparation of carbon dioxide-based polyols with different molecular weights is realized, the content of carbonate units in the prepared polyol is controllable, and the content of cyclic carbonate by-products is extremely low.
Description
Technical Field
The invention relates to poly (carbonate-ether) polyol and a preparation method thereof, belonging to the technical field of polymer preparation.
Background
The carbon dioxide-based polyol is a novel polyol which is synthesized by taking carbon dioxide as a raw material and has a carbonate bond and an ether bond structure, is mainly used as a raw material for polyurethane synthesis, has the advantages of greenness, environmental protection, low cost and the like due to the fact that the novel polyol is synthesized by taking cheap waste gas resource carbon dioxide as a raw material, is a novel polyol material with the most development potential, and is concerned by scientific research and industrial circles.
The most critical problem in the preparation of polyols from carbon dioxide and epoxy compounds is the design of the catalyst. Since the discovery of carbon dioxide copolymerization, catalyst research has been spotlighted as the most central factor limiting the development of this field, and many scientists have conducted a great deal of research to develop a series of catalyst systems. However, the preparation of carbon dioxide-based polyols requires the control of molecular weight by adding a chain transfer agent, so that the catalyst activity is more demanding, and the synthesis of high molecular weight carbon dioxide-based polymers was only possible at an early stage due to the low catalyst activity.
Until about 90 years in the last century, Double Metal Cyanide (DMC) catalysts applied in the field of alkylene oxide homopolymerization were applied to catalyze the copolymerization of carbon dioxide and alkylene oxide, so that the preparation of carbon dioxide-based polyols was successfully realized, and the rapid development of the field of synthesizing polymers by using carbon dioxide as a raw material was promoted. To date, the catalysts used in this field have been predominantly Double Metal Cyanide (DMC). Although the DMC system has the advantage of high activity compared with other catalyst systems, when the DMC system is used for catalyzing low-molecular-weight carbon dioxide-based polyol prepared by copolymerizing carbon dioxide and epoxide, the problems of difficult control of carbonate unit content (generally lower than 30 mol%), high content of cyclic carbonate serving as a byproduct and the like exist. Chinese patent application publication No. CN1060299A discloses preparation of aliphatic poly (carbonate-ether) polyol, which is prepared by using a high polymer supported bimetallic catalyst to catalyze the reaction of carbon dioxide and epoxide, but the obtained polymer has high ether segment content, and the carbonate content is lower than 30%. The Chinese patent with application publication number CN102206333A discloses a low molecular weight poly (carbonate-ether) polyol, a preparation method and application thereof, wherein a bimetallic complex catalyst is used for catalyzing carbon dioxide and propylene oxide to copolymerize to prepare the poly (carbonate-ether) polyol, the content of carbonate is increased to 45-60%, the content of ether segments is still higher, and the cyclic carbonate byproduct in the product reaches 3%.
The presence of cyclic by-products in the polyol product can affect the performance of the further prepared polyurethane material, so that the cyclic by-products must be removed in the production process, and the energy consumption in the purification process is greatly increased due to the high boiling point of the cyclic carbonate. Therefore, if an improved catalyst can be prepared, the content of the polycarbonate of the polyol can be controlled, and the cyclic by-products can be controlled to a lower level, the performance and the quality of the carbon dioxide-based polyol can be improved, and the scale application of the carbon dioxide-based polyol can be promoted.
Disclosure of Invention
In order to solve the technical problems, the invention provides a poly (carbonate-ether) polyol and a preparation method thereof, which can realize the high-efficiency preparation of carbon dioxide-based polyols with different molecular weights by the design and synthesis of a catalyst, and the prepared polyol has controllable carbonate unit content and extremely low content of cyclic carbonate by-products.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a bimetallic catalyst, which comprises the following steps:
(1) dissolving a metal cyanide complex compound by using a solvent, and stirring to obtain a metal cyanide complex compound solution S1;
(2) dissolving metal zinc salt and trace metal salt by using a solvent, and stirring to obtain a solution S2;
(3) placing the solution S2 in a carbon dioxide atmosphere, pressurizing, injecting the metal cyanide complex solution S1, stirring, centrifuging, pulping and washing to obtain a precipitate;
(4) and drying the precipitate in vacuum to constant weight to obtain the bimetallic catalyst.
Further, the pulping is to use poor solvent of the precipitate to stir the centrifuged precipitate into paste, and aims to wash away the solvent used in the reaction process and unreacted raw materials.
Further, the molar ratio of the metal cyanide complex to the metal zinc salt is 1: 1.5-10, and the molar ratio of the metal cyanide complex to the trace metal salt is 50-5000: 1.
Further, the metal cyanide complex is a water-soluble metal hydride, preferably one or more of potassium cobalt cyanide, potassium hexacyanoferrate and potassium hexacyanoruthenium (II), more preferably one or more of potassium cobalt cyanide and potassium hexacyanoferrate.
Further, the metal zinc salt is one or more of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate and zinc sulfate, preferably one or more of zinc chloride, zinc benzoate, zinc nitrate and zinc sulfate, and more preferably one or more of zinc chloride, zinc nitrate and zinc sulfate.
Further, the trace metal salt is one or more of zirconium chloride, zirconium acetylacetonate, ammonium zirconium carbonate, zirconium trifluoroacetylacetonate, cerium (III) nitrate hexahydrate, cerium bromide, cerium sulfate, cerous sulfate, ammonium cerium nitrate, cerium chloride, ruthenium trichloride, ruthenium acetylacetonate, indium trichloride, indium acetate, indium chloride, indium (III) nitrate hydrate, indium sulfate, cesium chloride, cesium oxalate, cesium nitrate, and cesium sulfate, and the trace metal salt can provide oxygen defects or metal defects, but the solubility of the trace metal salt is not a necessary factor for influencing the catalyst activity, and the insoluble or poorly soluble metal salt can also improve the performance of the bimetallic catalyst on the premise of providing defect sites.
Further, the solvent in the step (1) and the step (2) is deionized water or a mixed solvent composed of deionized water and alcohols and ether solvents in any proportion, wherein the alcohols are one or more of n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol and butanediol; the ethers are one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycerol, dimethyl ether, tetrahydrofuran and 1, 4-epoxy hexacyclic ring.
Further, the mass ratio of the metal cyanide complex to the solvent in the step (1) is 0.01-20: 1, the mass ratio of the metal zinc salt to the solvent in the step (2) is 0.01-10: 1.
further, the stirring time in the step (1) is 0.5-24 hours, the temperature is 20-120 ℃, the stirring time in the step (2) is 0.5-24 hours, the temperature is 0-120 ℃, the pressurizing pressure in the step (3) is 0.1-15 MPa, and the temperature is 20-150 ℃.
Further, the injection rate of the metal cyanide complex solution S1 in step (3) is 1mL/min to 500 mL/min.
The invention also provides the bimetallic catalyst prepared by the preparation method.
The invention also provides a preparation method of the poly (carbonate-ether) polyol, which comprises the following steps: and catalyzing the epoxy compound and the chain transfer agent to perform polymerization reaction by using the bimetallic catalyst under the condition of carbon dioxide pressure to obtain the poly (carbonate-ether) polyol.
Further, the epoxy compound is one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene oxide and 4-vinyl-1, 2-cyclohexene oxide; the chain transfer agent is one or more of water, small molecular alcohol, phenol, mercaptan, carboxylic acid, hydroxy acid and oligomer containing hydroxyl.
Further, the small molecular alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, decanediol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol or pentaerythritol; the phenol is preferably catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylenebiphenol, 4' - (2-methylpropylene) biphenol, 4- (2-ethylhexylene) biphenol, 2 '-methylenebiphenol, or 2,2' - (1, 2-cyclohexanediyl-dinitrosopropylene) biphenol; the thiol is preferably methyl mercaptan, dithiol or an oligomeric polythiol; the carboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid or oleic acid; the hydroxy acid is preferably lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric acid, citric acid or salicylic acid.
The mass ratio of the bimetallic catalyst to the epoxide is 1 (5000-2000000), preferably 1 (50000-2000000), more preferably 1 (1000000-2000000), and the molar ratio of the epoxide to the chain transfer agent is 100: 1-12.
Further, the pressure is 0.1-12 MPa, preferably 1-6 MPa, and more preferably 3-5 MPa; the temperature of the polymerization reaction is 20-150 ℃, preferably 50-120 ℃, more preferably 60-100 ℃, and the time of the polymerization reaction is 0.5-48 h, preferably 2-12 h, more preferably 3-8 h.
The invention also provides the poly (carbonate-ether) polyol prepared by the preparation method.
The preparation of the poly (carbonate-ether) polyols of the present invention may be carried out in high pressure polymerization reactors of various sizes, preferably under constant pressure and continuous stirring, such as at a speed of 500 rpm. After the polymerization reaction is finished, cooling the polymerization kettle to room temperature, discharging residual carbon dioxide, washing the polymer obtained by the polymerization reaction with water or an alcohol solvent, and drying to obtain a carbon dioxide-based polyol crude product.
The invention discloses the following technical effects:
1) the poly (carbonate-ether) polyol prepared by the method has lower weight content of cyclic carbonate and higher content of carbonate units, and is adjustable between 42 and 86 percent. Therefore, the catalyst provided by the invention has higher catalytic activity and better product selectivity, and the content of the carbonate unit is controllable.
2) According to the preparation method of the poly (carbonate-ether) polyol, the activity of the catalyst can be regulated and controlled between 2.9-15.9 kg of polyol/g of catalyst according to different types and dosage of chain transfer agents used in the preparation process, the activity of the catalyst is obviously improved, and the main reasons can be summarized into two aspects: firstly, the bimetallic catalyst is prepared in the carbon dioxide atmosphere, and the carbon dioxide enables the surface of the catalyst to form a carboxyl carbonyl group in the reaction, so that the activation and the adsorption of the carbon dioxide are facilitated; on the other hand, the introduction of trace metal elements such as zirconium, ruthenium, cerium, indium, cesium and the like contributes to the introduction of oxygen defects on the catalyst surface, and carbon dioxide is easily adsorbed to the surface having oxygen defects and passes through the carbon atomsThe atom is linked to an oxygen atom near the oxygen defect or one of its oxygen atoms is placed in an oxygen vacancy, whereby CO 2 The strong interaction between the oxygen atom in the (C) ═ O bond and the surface defect weakens to activate, so that the (C) ═ O bond is easier to break to accelerate the reaction. The two reasons are most intuitively shown as the improvement of the dissolving (adsorbing) capacity of the reaction system to the carbon dioxide, which provides possibility for realizing the high-efficiency catalysis of the copolymerization of the carbon dioxide and the alkylene oxide by the bimetallic catalyst to prepare the polyol.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated or intervening value in a stated range, and every other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The raw materials used in the examples of the present invention were all commercially available.
In the embodiment of the present invention, "slurrying" means that the centrifuged precipitate is stirred into a paste by using a poor solvent for the precipitate, and the solvent used in the reaction process and unreacted raw materials are washed away. The specific types of metal cyanide complex, metal zinc salt, trace metal salt, epoxy compound, and chain transfer agent used in the examples of the present invention are all preferable.
The technical solution of the present invention is further illustrated by the following examples.
Example 1
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 200g of zinc chloride and 0.0466g of zirconium chloride in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 8MPa, controlling the temperature in the kettle to be 40 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 0.5h after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitated product;
(4) the precipitated product was vacuum dried at 45 ℃ to constant weight and ground to obtain 472g of a bimetallic catalyst (DMC-Zr).
The elemental analysis results were: 21.8 wt% of Zn; 11.2 wt% of Co; 0.0091 wt% of Zr; 28.9 wt% of C; 3.1 wt% of H; 15.9 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 26nm and a concentration PDI value of 0.125.
Example 2
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 230g of zinc nitrate and 0.177g of indium acetate in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 1MPa, controlling the temperature in the kettle to be 40 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 2 hours after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitate;
(4) the precipitated product was dried In vacuo at 45 ℃ to constant weight and ground to obtain 456g of a bimetallic catalyst (DMC-In-1).
The elemental analysis results were: 22.3 wt% of Zn; 11.5 wt% of Co; 0.028 wt% of In; 29.3 wt% of C; 3.5 wt% of H; 15.3 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 35nm and a concentration PDI value of 0.159.
Example 3
(1) Dissolving 329g of potassium hexacyanoferrate in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 220g of zinc bromide and 0.177g of indium acetate in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 1MPa, controlling the temperature in the kettle to be 40 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 2 hours after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitate;
(4) and (3) drying the precipitate product at 45 ℃ In vacuum to constant weight, and grinding to obtain 426g of a bimetallic catalyst (DMC-In-2).
The elemental analysis results were: 23.4 wt% of Zn; 11.9 wt% of Fe; 0.020 wt% of In; 27.8 wt% of C; 3.6 wt% of H; 17.2 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 33nm and a concentration PDI value of 0.187.
Example 4
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 2 hours at 40 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 200g of zinc chloride and 0.082g of cerium chloride in 300ml of deionized water, and stirring for 1h at 40 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 0.5MPa, controlling the temperature in the kettle to be 60 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reaction for 1h after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitated product;
(4) the precipitated product was dried in vacuo at 45 ℃ to constant weight and ground to obtain 469g of a bimetallic catalyst (DMC-Ce).
The elemental analysis results were: 22.7 wt% of Zn; 11.8 wt% of Co; 0.008 wt% of Ce; 28.1 wt% of C; 3.8 wt% of H; 15.0 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 27nm and a concentration PDI value of 0.102.
Example 5
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 100g of zinc chloride, 100g of zinc acetylacetonate and 1.68g of cesium chloride in 300ml of deionized water, and stirring for 2 hours at the temperature of 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the kettle is in carbon dioxide atmosphere, pressurizing to 1MPa, controlling the temperature in the kettle to be 40 ℃, and injecting the solution S1 into the kettle at high pressure of 50mL/min through a plunger pumpIn the kettle solution S2, stirring and reacting for 4 hours after the injection is finished, decompressing the high-pressure kettle, centrifuging the product, and washing the product by tert-butyl alcohol slurry to obtain a precipitate product;
(4) and (3) drying the precipitated product in vacuum at the temperature of 45 ℃ to constant weight, and grinding to obtain 475g of bimetallic catalyst (DMC-Cs).
The elemental analysis results were: 20.5 wt% of Zn; 12.5 wt% of Co; 0.22 wt% of Cs; 26.3 percent by weight of C; 3.5 wt% of H; 16.8 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, which showed an average particle size of 34nm and a concentration PDI value of 0.156.
Examples 1 to 1
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 50mmol of dipropylene glycol and 2mol of propylene oxide were placed in a 500ml autoclave previously subjected to a water-removing and oxygen-removing treatment, and CO was charged 2 The reaction was stirred for 4h at a pressure of 2MPa and a temperature of 80 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 38.5g of poly (carbonate-ether) polyol, having a catalyst activity of 7.7kg of polyol/g of catalyst. The number average molecular weight of the polymer was 870g/mol as determined by gel permeation chromatography, and the molecular weight distribution was 1.09; 1H-NMR analysis showed 1.2% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 58%, and a titration hydroxyl value of 143.0.
Examples 1 to 2
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of 1, 4-cyclohexanediol and 2mol of propylene oxide are placed in a 500ml autoclave which has been freed from water and oxygen and is charged with CO 2 The reaction was stirred for 30h at a pressure of 4MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 25g of poly (carbonate-ether) polyol, having a catalyst activity of 5.0kg polyol/g catalyst. The number average molecular weight of the polymer was 1200g/mol, molecular weight distribution was 1.05 as determined by gel permeation chromatography; 1H-NMR analysis showed that the cyclic carbonate produced as a by-product was 0.95%, and polyThe carbonate unit content of the compound was about 65% and the titration hydroxyl number was 92.8.
Examples 1 to 3
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 30mmol of 1, 2-cyclohexanedimethanol and 1mol of propylene oxide are placed in a 500ml autoclave previously subjected to a water and oxygen removal treatment, and CO is introduced 2 The reaction is stirred for 8 hours at the temperature of 80 ℃ until the pressure is 2 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 60g of poly (carbonate-ether) polyol, having a catalyst activity of 12kg polyol/g catalyst. The number average molecular weight of the polymer was 1890g/mol, the molecular weight distribution was 1.08, as determined by gel permeation chromatography; 1H-NMR analysis showed 1.9% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 47%, and a titration hydroxyl value of 58.5.
Examples 1 to 4
5mg of the bimetallic catalyst DMC-In-1 prepared In example 2, 30mmol of hydroquinone and 2mol of propylene oxide are introduced into a 500ml autoclave previously freed from water and oxygen, and CO is introduced 2 The reaction was stirred for 8h at a pressure of 5MPa and a temperature of 60 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 48g of poly (carbonate-ether) polyol, having a catalyst activity of 9.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1500g/mol, the molecular weight distribution was 1.05 as determined by gel permeation chromatography; 1H-NMR analysis showed 0.9% cyclic carbonate by-product, about 72% carbonate units in the polymer and a titration hydroxyl number of 77.4.
Examples 1 to 5
5mg of the bimetallic catalyst DMC-In-2 prepared In example 3, 50mmol of dipropylene glycol and 1mol of propylene oxide were placed In a 500ml autoclave previously subjected to a water-removing and oxygen-removing treatment, and CO was charged 2 The reaction was stirred for 6h at 50 ℃ until the pressure was 5 MPa. After the polymerization reaction is finished, cooling the reaction kettle to room temperature, slowly discharging carbon dioxide to obtainThe product of (2) was dried under vacuum to remove unreacted propylene oxide to give 18g of poly (carbonate-ether) polyol having a catalyst activity of 3.6kg polyol/g catalyst. The polymer had a number average molecular weight of 5200g/mol and a molecular weight distribution of 1.05 as determined by gel permeation chromatography; 1H-NMR analysis showed 0.75% cyclic carbonate by-product, about 55% carbonate units in the polymer and a titration hydroxyl number of 21.6.
Examples 1 to 6
5mg of the bimetallic catalyst DMC-Ce prepared in example 4, 10mmol of dipropylene glycol and 1mol of propylene oxide were placed in a 500ml autoclave previously subjected to a dehydration and deoxygenation treatment, and CO was charged 2 The reaction was stirred for 24h at a pressure of 2MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 33g of poly (carbonate-ether) polyol, having a catalyst activity of 6.6kg of polyol/g of catalyst. The number average molecular weight of the polymer is 3200g/mol and the molecular weight distribution is 1.04 by gel permeation chromatography; 1H-NMR analysis showed 1.2% cyclic carbonate by-product, a carbonate unit content in the polymer of about 64%, and a titration hydroxyl value of 34.0.
Examples 1 to 7
5mg of the bimetallic catalyst DMC-Ce prepared in example 4, 20mmol of dipropylene glycol and 1mol of propylene oxide were placed in a 500ml autoclave previously subjected to a dehydration and deoxygenation treatment, and CO was charged 2 The reaction was stirred for 4h at 85 ℃ until the pressure was 2 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 48g of poly (carbonate-ether) polyol, having a catalyst activity of 9.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 2400g/mol, as determined by gel permeation chromatography, and the molecular weight distribution was 1.03; 1H-NMR analysis showed 1.2% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 86%, and a titration hydroxyl value of 146.5.
Examples 1 to 8
5mg of the bimetallic catalyst prepared in example 5DMC-Cs, 5mmol dipropylene glycol and 1mol propylene oxide are added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO is charged 2 The reaction was stirred for 4h at a pressure of 2MPa and a temperature of 75 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 18g of poly (carbonate-ether) polyol, having a catalyst activity of 3.6kg polyol/g catalyst. The number average molecular weight of the polymer is 3600g/mol and the molecular weight distribution is 1.08 by gel permeation chromatography; 1H-NMR analysis showed 2.9% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 42%, and a titration hydroxyl value of 32.5.
Examples 1 to 9
5mg of the bimetallic catalyst DMC-Cs prepared in example 5, 20mmol of dipropylene glycol and 1mol of propylene oxide (0.5mol) and cyclohexene oxide (0.5mol) were placed in a 500ml autoclave previously subjected to a water-removing and oxygen-removing treatment, and CO was charged 2 The reaction was stirred for 10h at a pressure of 4MPa and a temperature of 60 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 32g of poly (carbonate-ether) polyol, having a catalyst activity of 6.4kg polyol/g catalyst. The number average molecular weight of the polymer was 1600g/mol, the molecular weight distribution was 1.06, as determined by gel permeation chromatography; 1H-NMR analysis showed 1.1% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 82%, and a titration hydroxyl value of 70.2.
Examples 1 to 10
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of sebacic acid and 1mol of propylene oxide are placed in a 500ml autoclave which has been previously freed from water and oxygen and is charged with CO 2 The reaction was stirred for 3h at a pressure of 2MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 27g of poly (carbonate-ether) polyol having a catalyst activity of 5.4kg polyol/g catalyst. The determination is carried out by gel permeation chromatographyThe number average molecular weight of the polymer is 1800g/mol, and the molecular weight distribution is 1.12; 1H-NMR analysis showed 1.50% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 79%, and a titration hydroxyl value of 62.
Examples 1 to 11
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of trimesic acid and 1mol of propylene oxide are placed in a 500ml autoclave which has been previously freed from water and oxygen and is charged with CO 2 The reaction was stirred for 4h at a pressure of 4MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 25g of poly (carbonate-ether) polyol, with a catalyst activity of 5kg polyol/g catalyst. The number average molecular weight of the polymer was 1300g/mol and the molecular weight distribution was 1.03 as determined by gel permeation chromatography; 1H-NMR analysis showed 2.30% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 70%, and a titration hydroxyl value of 126.0.
Examples 1 to 12
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of pentaerythritol and 2mol of propylene oxide are placed in a 500ml autoclave which has been previously freed from water and oxygen and is charged with CO 2 The reaction was stirred for 4h at a pressure of 3MPa and a temperature of 80 ℃. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 29g of poly (carbonate-ether) polyol having a catalyst activity of 5.8kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1500g/mol, the molecular weight distribution was 1.08, as determined by gel permeation chromatography; 1H-NMR analysis showed 2.60% of cyclic carbonate by-product, about 63% of carbonate units in the polymer and a titration hydroxyl number of 145.5.
Examples 1 to 13
5mg of the bimetallic catalyst DMC-Ce prepared in example 4, 10mmol of citric acid and 1mol of propylene oxide are added into a 500ml autoclave which is previously subjected to water removal and oxygen removal treatment, and CO is charged 2 Controlling the temperature until the pressure is 2MPaThe reaction was stirred at 80 ℃ for 4 h. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 27g of poly (carbonate-ether) polyol having a catalyst activity of 5.4kg polyol/g catalyst. The number average molecular weight of the polymer was 2500g/mol, the molecular weight distribution was 1.09 by gel permeation chromatography; 1H-NMR analysis showed 2.2% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 68%, and a titration hydroxyl value of 89.9.
Examples 1 to 14
5mg of the bimetallic catalyst DMC-In-1 prepared In example 2, 10mmol of phloroglucinol and 1mol of propylene oxide are added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal In advance, and CO is filled into the kettle 2 The reaction was stirred for 4h at a pressure of 4MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 32g of poly (carbonate-ether) polyol, having a catalyst activity of 6.4kg polyol/g catalyst. The number average molecular weight of the polymer was 3300g/mol, molecular weight distribution 1.08, as determined by gel permeation chromatography; 1H-NMR analysis showed 2.15% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 64%, and a titration hydroxyl value of 51.0.
Comparative example 1
Step (1) the same as in preparation example 1;
(2) dissolving 200g of zinc chloride in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 15MPa, controlling the temperature in the kettle to be 20 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 0.5h after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitated product;
(4) and (3) drying the precipitated product at 45 ℃ in vacuum to constant weight, and grinding to obtain 1465 g of the bimetallic catalyst DMC-DMC.
The elemental analysis results were: 22.5 wt% of Zn; 10.8 wt% of Co; 27.9 wt% of C; 3.3 wt% of H; 16.2 wt% of N. The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 29nm and a concentration PDI value of 0.106.
Comparative examples 1 to 1
5mg of the bimetallic catalyst DMC-1 prepared in comparative example 1, 50mmol of dipropylene glycol and 2mol of propylene oxide were charged into a 500ml autoclave previously subjected to water and oxygen removal treatment (polymerization conditions were the same as in example 1, only the catalyst was changed), and CO was charged 2 The reaction was stirred for 4h at a pressure of 2MPa and a temperature of 80 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 10.5g of poly (carbonate-ether) polyol, having a catalyst activity of 2.1kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1050g/mol and the molecular weight distribution was 1.12 as determined by gel permeation chromatography; 1H-NMR analysis showed that the cyclic carbonate by-product was 3.6%, the carbonate unit content in the polymer was about 41%, and the titration hydroxyl value was 107.5.
Comparative examples 1 to 2
5mg of the bimetallic catalyst DMC-In-1 prepared In preparation example 2, 30mmol of hydroquinone and 2mol of propylene oxide were charged into a 500ml autoclave which had been previously freed from water and oxygen (polymerization conditions were the same as In example 4, only the catalyst was changed), CO was charged 2 The reaction was stirred for 8h at a pressure of 5MPa and a temperature of 60 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 9.8g of poly (carbonate-ether) polyol, having a catalyst activity of 1.96kg of polyol/g of catalyst. The number average molecular weight of the polymer was 950g/mol, the molecular weight distribution was 1.09, as determined by gel permeation chromatography; the 1H-NMR analysis showed that the cyclic carbonate by-product was 3.9%, the carbonate unit content in the polymer was about 39%, and the titration hydroxyl value was 118.
Comparative examples 1 to 3
5mg of the bimetallic catalyst DMC-1 prepared in comparative example 1, 20mmol of dipropylene glycol and 1mol of epoxyPropane was charged into a 500ml autoclave previously subjected to water removal and oxygen removal (polymerization conditions were the same as in example 7, only the catalyst was changed), CO was introduced 2 The reaction was stirred for 4h at 85 ℃ until the pressure was 2 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 10.6g of poly (carbonate-ether) polyol, having a catalyst activity of 2.12kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1200g/mol, molecular weight distribution was 1.15 as determined by gel permeation chromatography; 1H-NMR analysis showed that the cyclic carbonate by-product was 8.9%, the carbonate unit content in the polymer was about 32%, and the titration hydroxyl value was 93.5.
From the above, it can be seen that, according to the different types and amounts of the chain transfer agents used in the preparation process, the catalyst activity can be regulated and controlled between 2.9-15.9 kg of polyol/g of catalyst, and the catalyst activity is obviously improved, and the main reasons can be summarized into two aspects: firstly, the bimetallic catalyst is prepared in the carbon dioxide atmosphere, and the carbon dioxide enables the surface of the catalyst to form a carboxyl carbonyl group in the reaction, so that the activation and the adsorption of the carbon dioxide are facilitated; on the other hand, the introduction of trace metal elements such as zirconium, ruthenium, cerium, indium, cesium and the like contributes to the introduction of oxygen defects on the catalyst surface, carbon dioxide is easily adsorbed to the presence of surface oxygen defects, and CO is bonded to an oxygen atom in the vicinity of the oxygen defects through a carbon atom or one of its oxygen atoms is placed in an oxygen vacancy, whereby CO 2 The strong interaction between the oxygen atom in the (C) ═ O bond and the surface defect weakens to activate, so that the (C) ═ O bond is easier to break to accelerate the reaction. The two reasons are most intuitively shown as the improvement of the dissolving (adsorbing) capacity of the reaction system to the carbon dioxide, which provides possibility for realizing the high-efficiency catalysis of the copolymerization of the carbon dioxide and the alkylene oxide by the bimetallic catalyst to prepare the polyol.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of a bimetallic catalyst is characterized by comprising the following steps:
(1) dissolving a metal cyanide complex compound by using a solvent, and stirring to obtain a metal cyanide complex compound solution S1;
(2) dissolving metal zinc salt and trace metal salt by using a solvent, and stirring to obtain a solution S2;
(3) placing the solution S2 in a carbon dioxide atmosphere, pressurizing, injecting the metal cyanide complex solution S1, stirring, centrifuging, pulping and washing to obtain a precipitate;
(4) and drying the precipitate in vacuum to constant weight to obtain the bimetallic catalyst.
2. The method according to claim 1, wherein the molar ratio of the metal cyanide complex to the metal zinc salt is 1:1.5 to 10, and the molar ratio of the metal cyanide complex to the trace metal salt is 50 to 5000: 1.
3. The production method according to claim 1, wherein the metal cyanide complex is a water-soluble metal cyanide complex; the metal zinc salt is one or more of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate and zinc sulfate; the trace metal salt is one or more of zirconium chloride, zirconium acetylacetonate, ammonium zirconium carbonate, zirconium trifluoroacetylacetonate, cerium (III) nitrate hexahydrate, cerium bromide, cerium sulfate, cerous sulfate, ammonium ceric nitrate, cerium chloride, ruthenium trichloride, ruthenium acetylacetonate, indium trichloride, indium acetate, indium chloride, indium (III) nitrate hydrate, indium sulfate, cesium chloride, cesium oxalate, cesium nitrate and cesium sulfate.
4. The method according to claim 1, wherein the stirring time in step (1) is 0.5 to 24 hours and the temperature is 20 to 120 ℃, the stirring time in step (2) is 0.5 to 24 hours and the temperature is 0 to 120 ℃, the pressure for pressurizing in step (3) is 0.1 to 15MPa and the temperature is 20 to 150 ℃.
5. A bimetallic catalyst prepared by the preparation method of any one of claims 1 to 4.
6. A method of preparing a poly (carbonate-ether) polyol, comprising the steps of: catalyzing the polymerization of an epoxy compound and a chain transfer agent with the bimetallic catalyst of claim 5 under carbon dioxide pressure conditions to provide the poly (carbonate-ether) polyol.
7. The preparation method according to claim 6, wherein the epoxy compound is one or more of ethylene oxide, propylene oxide, 1, 2-epoxybutane, cyclohexene oxide, cyclopentane epoxide, chloropropylene oxide, glycidyl methacrylate ether, methyl glycidyl ether, phenyl glycidyl ether, styrene oxide, 4-vinyl-1, 2-epoxycyclohexane; the chain transfer agent is one or more of water, small molecular alcohol, phenol, mercaptan, carboxylic acid, hydroxy acid and oligomer containing hydroxyl.
8. The preparation method of claim 6, wherein the mass ratio of the bimetallic catalyst to the epoxide is 1 (5000-2000000), and the molar ratio of the epoxide to the chain transfer agent is 100: 1-12.
9. The preparation method according to claim 6, wherein the pressure is 0.1 to 12MPa, the temperature of the polymerization reaction is 20 to 150 ℃, and the time is 0.5 to 48 hours.
10. A poly (carbonate-ether) polyol prepared by the method of any one of claims 6 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210548812.4A CN114805781B (en) | 2022-05-20 | 2022-05-20 | Poly (carbonate-ether) polyol and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210548812.4A CN114805781B (en) | 2022-05-20 | 2022-05-20 | Poly (carbonate-ether) polyol and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114805781A true CN114805781A (en) | 2022-07-29 |
CN114805781B CN114805781B (en) | 2023-10-27 |
Family
ID=82516191
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210548812.4A Active CN114805781B (en) | 2022-05-20 | 2022-05-20 | Poly (carbonate-ether) polyol and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114805781B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115490843A (en) * | 2022-11-07 | 2022-12-20 | 科丰兴泰(杭州)生物科技有限公司 | Comprehensive recycling method and application of waste lithium iron phosphate batteries |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1304946A (en) * | 2000-08-16 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Composite catalyst bimetal cyanide and its preparing process and application |
CN102617844A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
CN102731766A (en) * | 2012-07-24 | 2012-10-17 | 中国科学院长春应用化学研究所 | Preparation method of aliphatic polycarbonate polyol |
CN103360589A (en) * | 2012-04-05 | 2013-10-23 | 中国石油天然气股份有限公司 | Multi-metal cyanide catalyst and preparation and application thereof |
CN110603279A (en) * | 2017-03-01 | 2019-12-20 | 伊克尼克技术有限公司 | Method for producing polyether carbonates |
CN112029083A (en) * | 2020-08-26 | 2020-12-04 | 烟台大学 | Polyether carbonate polyol and preparation method thereof |
-
2022
- 2022-05-20 CN CN202210548812.4A patent/CN114805781B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1304946A (en) * | 2000-08-16 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Composite catalyst bimetal cyanide and its preparing process and application |
CN102617844A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
CN103360589A (en) * | 2012-04-05 | 2013-10-23 | 中国石油天然气股份有限公司 | Multi-metal cyanide catalyst and preparation and application thereof |
CN102731766A (en) * | 2012-07-24 | 2012-10-17 | 中国科学院长春应用化学研究所 | Preparation method of aliphatic polycarbonate polyol |
CN110603279A (en) * | 2017-03-01 | 2019-12-20 | 伊克尼克技术有限公司 | Method for producing polyether carbonates |
CN112029083A (en) * | 2020-08-26 | 2020-12-04 | 烟台大学 | Polyether carbonate polyol and preparation method thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115490843A (en) * | 2022-11-07 | 2022-12-20 | 科丰兴泰(杭州)生物科技有限公司 | Comprehensive recycling method and application of waste lithium iron phosphate batteries |
Also Published As
Publication number | Publication date |
---|---|
CN114805781B (en) | 2023-10-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2658895B1 (en) | Alkylene oxide polymerization using a double metal cyanide catalyst complex and a magnesium, group 3-group 15 metal or lanthanide series metal compound | |
CA2306378C (en) | Crystalline double metal cyanide catalysts for producing polyether polyols | |
US6429342B1 (en) | Polymerization of ethylene oxide using metal cyanide catalysts | |
JPH04145123A (en) | Production of polyether compound | |
US6642423B2 (en) | Polymerization of ethylene oxide using metal cyanide catalysts | |
CN114805781B (en) | Poly (carbonate-ether) polyol and preparation method thereof | |
CN102040731B (en) | Method for preparing polyether polyol | |
CN112126053B (en) | Preparation method and application of double metal cyanide catalyst | |
CN101003622A (en) | Catalyst of load type bimetallic cyaniding complex, preparation method and application | |
US6093793A (en) | Process for the production of polyether polyols | |
CA2328453C (en) | Method for producing long-chain polyetherpolyols without reprocessing | |
CN101302287B (en) | Method for preparing polyether polyol by continuous process | |
JP4574964B2 (en) | Activated starting mixture and related methods | |
CN112625231B (en) | Catalyst for preparing polyol, preparation method and application thereof | |
CN115073723B (en) | Separable catalyst and preparation method of low-molecular-weight narrow-distribution colorless poly (carbonate-ether) polyol | |
CN115028845B (en) | Zinc coordination polymer catalyst and preparation method and application thereof | |
CA2338657A1 (en) | Bimetallic-cyanide catalysts used for preparing polyether polyols | |
KR20010101746A (en) | Method for Preparing Polyether Polyols | |
CA2372335A1 (en) | Double metal cyanide catalysts for the production of polyether polyols | |
CN101302286B (en) | Multi-metal cyanide complex catalyst | |
CN114736365B (en) | Preparation method, product and application of bimetallic catalyst | |
JP2008138209A (en) | Continuous processes for the production of alkylphenol ethoxylates | |
CN103881077B (en) | The preparation method of poly-(carbonic ether-ether) trivalent alcohol | |
US20030211935A1 (en) | Double-metal cyanide catalysts for preparing polyether polyols | |
CN114433098B (en) | Catalyst, preparation method thereof and method for reducing aldehyde content in polyether polyol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |