CN116874761A - Process for preparing low unsaturation, high activity polyether polyols - Google Patents
Process for preparing low unsaturation, high activity polyether polyols Download PDFInfo
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- CN116874761A CN116874761A CN202210362158.8A CN202210362158A CN116874761A CN 116874761 A CN116874761 A CN 116874761A CN 202210362158 A CN202210362158 A CN 202210362158A CN 116874761 A CN116874761 A CN 116874761A
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- Prior art keywords
- polyether polyol
- unsaturation
- high activity
- preparing
- low
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- 229920000570 polyether Polymers 0.000 title claims abstract description 72
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 71
- 229920005862 polyol Polymers 0.000 title claims abstract description 55
- 150000003077 polyols Chemical class 0.000 title claims abstract description 55
- 230000000694 effects Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- -1 hydrogen compound Chemical class 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 13
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 26
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 7
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- 239000008121 dextrose Substances 0.000 claims description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 229940113120 dipropylene glycol Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003017 phosphorus Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005871 reactive polyether polyol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004072 triols Chemical class 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
- 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
- C08G65/2603—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 the other compounds containing oxygen
- C08G65/2606—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 the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
Abstract
The invention relates to a method for preparing polyether polyol with low unsaturation degree and high activity, which mainly solves the problem that an alkali catalyst used in the production of polyether polyol in the prior art cannot simultaneously meet the low unsaturation degree and the high activity. The invention prepares the low-unsaturation and high-activity polyether polyol by adopting a method for preparing the low-unsaturation and high-activity polyether polyol, adopting organophosphorus alkoxide as a catalyst and using an active hydrogen compound and alkylene oxide to carry out polymerization reaction; the active hydrogen compound is an organic compound containing hydroxyl groups, is selected from hydroxyl alcohols, saccharides or derivatives thereof with 2-20 carbon atoms and 1-8 hydroxyl groups or polyether polyols with 2-8 hydroxyl groups and number average molecular weight of 200-5000, and can be used in the preparation of polyether polyols.
Description
Technical Field
The present invention relates to a process for preparing low unsaturation, high activity polyether polyols.
Background
Polyether polyol is one of the main raw materials for synthesizing polyurethane materials, and the preparation methods of the polyether polyol are numerous and mainly comprise anionic polymerization, cationic polymerization, coordination polymerization and the like. CN201410061357.0 relates to a process for preparing polyether polyols, based on primer compounds which are solid at room temperature, a process for solvent-free preparation of polyether polyols having a block polyether chain structure; anionic polymerization utilizes an inorganic strong base (e.gKOH) is a catalyst, and inorganic strong base has the advantages of low cost, easy removal in polyether polyol and the like, and is widely applied to industrial production when preparing low molecular weight polyether polyol; however, inorganic strong bases tend to isomerize propylene oxide to produce monohydroxy polyethers having terminal unsaturated double bonds, which reduce the functionality and relative molecular weight of the polyether polyols, especially when preparing high molecular weight products, which are highly abundant; for example, in the preparation of polyether triols having a trifunctional relative molecular weight of 5000, the unsaturation levels are above 0.05 mol/kg; cationic polymerization utilizes strong lewis acids (e.g., BF 3 Diethyl ether) is used as a catalyst, and by-products with dioxane structures are formed during the polymerization of alkylene oxides, which have adverse effects on the performance of the prepared polyurethane products, and impurities need to be removed by using a complicated process, so that the method is basically not used in industrial production; although double metal cyanide complex catalysts are very active in propylene oxide homopolymerization and ethylene oxide/propylene oxide random copolymerization, polyether polyols with high molecular weight can be prepared, but small-molecular polyols (such as glycerol) cannot be directly used as an initiator, and particularly when the double metal cyanide complex catalysts are used for ethylene oxide homopolymerization, the double metal cyanide complex catalysts can cause ethylene oxide to undergo self-polymerization reaction to generate byproducts of polyethylene oxide, so that the performance of the polyether polyol is affected.
The high activity polyether polyol is a polyether polyol with primary hydroxyl (-CH) 2 OH) structure, the most widely used polyether triol with the number average molecular weight of 4500-6000 is mainly applied to preparing high-resilience polyurethane foam plastic; the preparation of high resilience polyurethane foams generally employs two methods, one is the reaction of a high activity polyether polyol with Toluene Diisocyanate (TDI), the number average molecular weight of such high activity polyether polyol is generally between 4500 and 5000; the other is to react the high-activity polyether polyol with diphenylmethane diisocyanate (MDI), the number average molecular weight of the high-activity polyether polyol is more required, and is usually more than 6000; the TDI system has the advantages of stable process, excellent product performance, high rebound resilience and the like, but the TDI has high toxicity and small reaction activity, so that the production environment is causedPoor curing speed, low hardness of low density foam, and the like; MDI systems, although having the disadvantages of high density, low rebound resilience and poor tear properties, have been sought to synthesize a low unsaturation, high molecular weight, high activity polyether polyol for use in the preparation of foams having low density, high rebound resilience and good tear properties by reaction with MDI, due to the low toxicity, high reactivity and low atomization properties of MDI.
Disclosure of Invention
The invention aims to solve the technical problem that the alkali catalyst used in the production of polyether polyol in the prior art cannot simultaneously meet the requirements of low unsaturation degree and high activity, and provides a novel method for preparing low unsaturation degree and high activity polyether polyol.
In order to solve the problems, the invention adopts the following technical scheme: a method for preparing low-unsaturation and high-activity polyether polyol adopts organophosphorus alkoxide as a catalyst and adopts an active hydrogen compound and alkylene oxide to carry out polymerization reaction to prepare the low-unsaturation and high-activity polyether polyol; the organic phosphorus alkoxide has a structural general formula (1) as follows:
wherein Ph is aryl or heteroatom group substituted aryl, R is alkyl of 1-4 carbon atoms; the active hydrogen compound is an organic compound containing hydroxyl groups and is selected from hydroxyl alcohols, saccharides or derivatives thereof with 2-20 carbon atoms and 1-8 hydroxyl groups or polyether polyols with 2-8 hydroxyl groups and number average molecular weight of 200-5000.
In the above technical solution, preferably, the alkylene oxide is at least one selected from ethylene oxide, propylene oxide, 1, 2-butylene oxide or styrene oxide; the low unsaturation, high activity polyether polyol is selected from at least two block copolymers of ethylene oxide, propylene oxide, 1, 2-butylene oxide or styrene oxide, and the molecular chain end is-CH 2 OH structure, unsaturation degree less than 0.04mol/kg, number average molecular weight more than 1000 times of the number of hydroxyl groups, primary hydroxyl group content more than 85%.
In the above technical scheme, more preferably, the unsaturation degree of the low-unsaturation degree and high-activity polyether polyol is 0.01-0.035mol/kg, and the primary hydroxyl content is more than 88%.
In the above technical scheme, most preferably, the unsaturation degree of the low-unsaturation degree and high-activity polyether polyol is 0.01-0.03mol/kg, and the primary hydroxyl content is more than 90%.
In the above technical scheme, preferably, the organophosphorus alkoxide is obtained by reacting an organophosphorus salt of the general formula (3) with an inorganic alcohol base, the organophosphorus salt of the general formula (3) is obtained by reacting phosphorus trichloride with an imine compound of the general formula (2),
wherein Ph is aryl or heteroatom group substituted aryl, n is an integer of 1-3, and A is an anion of inorganic salt.
In the above technical solution, more preferably, the inorganic alcohol base has a structure of general formula (4):
M + RO - (4)
wherein M is + Is an alkali metal ion; r is an alkyl group of 1 to 4 carbon atoms.
In the above embodiment, more preferably, the anion of the inorganic salt is selected from NO 3 - 、SO 4 2- 、PO 4 2- 、X - 、Cr 2 O 7 2- 、CO 3 2- Or BF 4 - Wherein X is halogen.
In the above embodiment, most preferably, the anion of the inorganic salt is selected from X - Or BF 4 - Wherein X is halogen.
In the above technical solution, preferably, the polymerization reaction conditions are: the temperature is 50-160 ℃, the reaction pressure is-0.05-3.0 MPa, and the reaction time is less than 50 hours.
In the above technical solution, preferably, the active hydrogen compound is at least one selected from ethylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, glycerol, trimethylolpropane, diglycerol, trimethylol melamine, pentaerythritol, glucose, sorbitol, dextrose, fructose or sucrose; the alkylene oxide is at least one of ethylene oxide, propylene oxide, 1, 2-butylene oxide or styrene oxide.
The low unsaturation, reactive polyether polyols of the present invention have high practical functionality and show little decrease with increasing molecular weight.
The specific implementation process is as follows:
firstly, synthesizing organic phosphorus alkoxide represented by a structural general formula (1), wherein Ph can be the same or different aryl or heteroatom substituted aryl, specifically Ph can be phenyl, p-chlorophenyl, p-bromophenyl, p-iodophenyl or p-nitrophenyl, most preferably phenyl, and R is alkyl with 1-4 carbon atoms, preferably methyl.
Reacting an imine compound having the general formula (2) with phosphorus trichloride in the presence of an aromatic hydrocarbon solvent at a low temperature to produce an organic phosphorus salt having the general structural formula (3), wherein the organic phosphorus salt is selected from the following compounds, for example: tris (benzophenone-imino) phosphonium chloride and tris [ bis (4-chloro) benzophenone-imino]Phosphonium chloride, tris [ di (4-bromo) benzophenone imino]Phosphonium chloride, tris [ di (4-iodo) benzophenone imino group]Phosphonium chloride and tris [ di (4-nitro) benzophenone imino]Phosphonium chloride and the like; the anions of these salts can also be converted to NO 3 - 、SO 4 2- 、PO 4 2- 、Cr 2 O 7 2- 、CO 3 2- Or BF 4 - The method comprises the steps of carrying out a first treatment on the surface of the Then the organic phosphorus salt reacts with inorganic alcohol alkali selected from alkali metal or alkaline earth metal to generate organic phosphorus alkoxide with the general formula (1); the inorganic alcohol base comprises potassium methoxideSodium methoxide, potassium ethoxide, potassium propoxide, sodium propoxide, potassium butoxide, sodium butoxide, and the like; the organic phosphorus salt is prepared by reacting imine compounds with the general formula (2) with phosphorus trihalide; the inorganic alkoxide has a structure of the general formula (4), wherein M + Is an alkali metal or alkaline earth metal ion; r is an alkyl group of 1 to 4 carbon atoms.
The low-unsaturation and high-activity polyether polyol is prepared by using organophosphorus alkoxide as a catalyst and carrying out polymerization reaction on an active hydrogen-containing compound and alkylene oxide at a certain temperature and under a certain pressure; in the present invention, the active hydrogen-containing compound means an organic compound containing a hydroxyl group, and is selected from the group consisting of: hydroxy alcohols having 2 to 20 carbon atoms and 1 to 8 hydroxyl groups, saccharides or derivatives thereof, for example: ethylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, glycerol, trimethylolpropane, diglycerol, trimethylol melamine, pentaerythritol, glucose, sorbitol, dextrose, fructose, sucrose, and the like, polyether polyols having a molecular weight of 200 to 5000 and a hydroxyl number of 2 to 8; in the present invention, the alkylene oxide includes ethylene oxide, propylene oxide, 1, 2-butylene oxide and styrene oxide or a mixture thereof, and the alkylene oxide is added in stages, and the latter stage must be ethylene oxide.
In the present invention, the amount of the organophosphorous alkoxide is not particularly limited, but the amount is usually 1X 10 -6 —5×10 -3 g/mol alkylene oxide, preferably 5X 10 -5 —2×10 -3 g/mol alkylene oxide.
In the present invention, the temperature of the polymerization reaction is selected to be in the range of 50 to 160 ℃, preferably 70 to 130 ℃, more preferably 70 to 90 ℃; the polymerization pressure is selected to be in the range of-0.05 to 3.0MPa, preferably 0.01 to 1MPa, more preferably 0.05 to 0.5 MPa; the polymerization time is selected to be within 50 hours, preferably within 1 to 30 hours, more preferably within 2 to 24 hours.
The polyether polyol prepared in the present invention may be used after removing the organophosphorus alkoxide catalyst by a conventional refining method, for example, an adsorption method or an acid type ion exchange resin treatment.
In the invention, as the novel organophosphorus alkoxide is adopted as the catalyst for preparing polyether polyol, the organophosphorus alkoxide catalyst can be used for preparing polyether polyol at a lower temperature, and has the characteristics of low unsaturation degree and high activity, for example, when the molecular weight of polyether triol reaches 7500, the unsaturation degree is less than 0.03mol/kg. The polyether polyol is more suitable for an MDI foam system, and achieves better technical effects.
The present invention is further illustrated by, but not limited to, the following examples.
Detailed Description
[ example 1 ]
137.5g of phosphorus trichloride and 1000ml of o-dichlorobenzene are added into a 3000ml three-neck flask provided with a stirrer, a thermometer and a dropping funnel, 918g of benzophenone imine is slowly added dropwise under the protection of nitrogen, the reaction temperature is controlled at 18 ℃, the temperature is slowly raised to normal temperature after the dropwise addition is finished, the mixture is stirred for 4 hours at normal temperature, the precipitate is removed by filtration, 75g of sodium methoxide and 400ml of methanol are added into the obtained solution, the mixture is reacted for 5 hours at 50 ℃, the methanol is removed by reduced pressure distillation, the precipitate is removed by filtration, and the catalyst A with the mass of 461.3g is obtained.
[ example 2 ]
Adding 68.75g phosphorus trichloride and 1000ml o-dichlorobenzene into a 3000ml three-neck flask equipped with a stirrer, a thermometer and a dropping funnel, slowly dropwise adding 454g benzophenone imine under the protection of nitrogen, controlling the reaction temperature at 18 ℃, slowly raising the temperature to normal temperature after the dropwise addition is finished, stirring for 2.5 hours at normal temperature, filtering to remove precipitate, decompressing the obtained solution to remove o-dichlorobenzene, and adding 10% wtNaBF 4 The mixture was reacted at 45℃for 2.5 hours, cooled to 10℃or lower to give a white solid, 35.0g of potassium methoxide and 200ml of methanol were added to the obtained solid, reacted at room temperature for 5 hours, and after centrifuging the solid, methanol was distilled off under reduced pressure at 50℃to give 256.2g of catalyst B.
[ example 3 ]
According to the conditions and procedure described in example 2, 10% by weight of Na 2 CO 3 Is used instead of NaBF 4 Catalyst C was obtained in a mass of 244.0g.
[ example 4 ]
Catalyst D, having a mass of 457.7g, was obtained by substituting bis (4-bromo) benzophenone imine for benzophenone imine according to the conditions and procedures described in example 2.
[ example 5 ]
Catalyst E, 371.0g in mass, was obtained by substituting bis (4-nitro) benzophenone imine for benzophenone imine according to the conditions and procedures described in example 2.
[ example 6 ]
Adding 1.98g of catalyst A and 16.8g of glycerin into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, when the oxygen content is less than 150ppm, vacuumizing until the pressure of the reaction kettle is reduced to 0.09MPa, slowly adding 1160g of propylene oxide when the temperature is increased to 90 ℃, controlling the reaction pressure to be less than 0.4MPa, continuously stirring until the pressure of the reaction kettle is not changed after the propylene oxide is added, slowly adding 230g of ethylene oxide, and obtaining 1401g of light yellow crude polyether triol after the reaction is finished. And neutralizing the obtained crude polyether triol by phosphoric acid, dehydrating and adsorbing by magnesium silicate to obtain the refined polyether triol. The hydroxyl value is 22.9mgKOH/g, the unsaturation degree is 0.027mol/Kg, the primary hydroxyl content is 90.6 percent, the theoretical functionality is 3.00, and the actual functionality is 2.64.
[ example 7 ]
1.87g of catalyst B and 16.8g of glycerin are added into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, after oxygen is removed by vacuumizing and nitrogen replacement, 1160g of propylene oxide is slowly added at the temperature of 85 ℃ after the oxygen content is less than 150ppm, and the reaction pressure is controlled to be less than 0.4Mpa. After the reaction of propylene oxide is finished, 230g of ethylene oxide is slowly added, 1396.0g of light yellow crude polyether triol is obtained after the reaction is finished, the hydroxyl value is 23.1mgKOH/g, the unsaturation degree is 0.025mol/Kg, the primary hydroxyl content is 91.0%, the theoretical functionality is 3.00, and the actual functionality is 2.73.
[ example 8 ]
Catalyst C was used instead of catalyst B according to the conditions and procedure described in example 7. A purified polyether triol was obtained having a hydroxyl number of 23.5mgKOH/g, a degree of unsaturation of 0.028mol/Kg, a primary hydroxyl content of 88.7%, a theoretical functionality of 3.00 and an actual functionality of 2.62.
[ example 9 ]
Catalyst B was replaced with 2.6g of catalyst D according to the conditions and procedure described in example 7. A purified polyether triol was obtained having a hydroxyl number of 23.5mgKOH/g, a degree of unsaturation of 0.031mol/Kg, a primary hydroxyl content of 89.3%, a theoretical functionality of 3.00 and an actual functionality of 2.60.
[ example 10 ]
Catalyst B was replaced with 3.1g of catalyst E according to the conditions and procedure described in example 7. A purified polyether triol was obtained having a hydroxyl number of 24.1mgKOH/g, a degree of unsaturation of 0.033mol/Kg, a primary hydroxyl content of 88.0%, a theoretical functionality of 3.00 and an actual functionality of 2.52.
[ example 11 ]
Adding 1.62g of catalyst B and 16.8g of glycerin into a 2L high-pressure reaction kettle with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, when the oxygen content is less than 150ppm, vacuumizing until the pressure of the reaction kettle is reduced to 0.09MPa, slowly adding 1160g of propylene oxide when the temperature is raised to 88 ℃, controlling the reaction pressure to be less than 0.4MPa, slowly adding 230g of ethylene oxide after the propylene oxide is added, obtaining 1390.0g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 23.1mgKOH/g, the unsaturation degree is 0.028mol/kg, the primary hydroxyl content is 91.1%, the theoretical functionality is 3.00, and the actual functionality is 2.64.
[ example 12 ]
According to the conditions and procedures described in example 11, 16.8g of glycerin was replaced with 24.5g of trimethylolpropane, and after the completion of the reaction, a purified polyether triol was obtained having a hydroxyl value of 22.9mgKOH/g, a degree of unsaturation of 0.027mol/kg, a primary hydroxyl group content of 91.3%, a theoretical functionality of 3.00 and an actual functionality of 2.71.
[ example 13 ]
Adding 1.8g of catalyst B and 16.8g of glycerin into a 2L high-pressure reaction kettle with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, slowly adding 1160g of propylene oxide at the temperature of 125 ℃ after the oxygen content is less than 150ppm, controlling the reaction pressure to be less than 0.4MPa, slowly adding 230g of ethylene oxide after the reaction of the propylene oxide is finished, obtaining 1392.8g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 23.5mgKOH/g, the unsaturation degree is 0.029mol/kg, the primary hydroxyl content is 89.8%, the theoretical functionality is 3.00 and the actual functionality is 2.64 after the refining.
[ example 14 ]
Adding 1.2g of catalyst B and 16.8g of glycerin into a 2L high-pressure reaction kettle provided with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, slowly adding 759g of propylene oxide at the temperature of 90 ℃ after the oxygen content is less than 150ppm, controlling the reaction pressure to be less than 0.4MPa, slowly adding 137g of ethylene oxide after the reaction of the propylene oxide is finished, obtaining 912.0g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 34.2mgKOH/g after refining, the unsaturation degree is 0.017mol/kg, the primary hydroxyl content is 84.5%, the theoretical functionality is 3.00 and the actual functionality is 2.83.
[ comparative example 1 ]
Adding 4.2g KOH and 16.8g glycerin into a 2L high-pressure reaction kettle with a thermometer, a pressure gauge and a stirrer, vacuumizing and replacing with nitrogen to remove oxygen, when the oxygen content is less than 150ppm, heating to 120 ℃, vacuumizing and dehydrating for 1h, slowly adding 1160g propylene oxide, controlling the reaction pressure to be less than 0.4MPa, slowly adding 230g ethylene oxide after the propylene oxide is added, obtaining 1389g of light yellow crude polyether triol after the reaction is finished, wherein the hydroxyl value is 25.0mgKOH/g, the unsaturation degree is 0.088mol/kg, the primary hydroxyl content is 87.2%, the theoretical functionality is 3.00, and the actual functionality is 2.15 after the refining.
[ comparative example 2 ]
According to the conditions and procedure described in example 14, using 2.74g KOH instead of 1.2g catalyst B, vacuum dehydration was carried out at 120℃for 1 hour to give a purified polyether triol having a hydroxyl number of 36.2mgKOH/g, an unsaturation degree of 0.068mol/kg, a primary hydroxyl group content of 76.4%, a theoretical functionality of 3.00 and an actual functionality of 2.49.
Claims (10)
1. A method for preparing low-unsaturation and high-activity polyether polyol adopts organophosphorus alkoxide as a catalyst and adopts an active hydrogen compound and alkylene oxide to carry out polymerization reaction to prepare the low-unsaturation and high-activity polyether polyol; the structural general formula (1) of the organophosphorus alkoxide is as follows:
wherein Ph is aryl or heteroatom group substituted aryl, R is alkyl of 1-4 carbon atoms; the active hydrogen compound is an organic compound containing hydroxyl groups and is selected from hydroxyl alcohols, saccharides or derivatives thereof with 2-20 carbon atoms and 1-8 hydroxyl groups or polyether polyols with 2-8 hydroxyl groups and number average molecular weight of 200-5000.
2. The method for preparing a low unsaturation, high activity polyether polyol according to claim 1, wherein the alkylene oxide is selected from at least one of ethylene oxide, propylene oxide, 1, 2-butylene oxide, or styrene oxide; the low unsaturation, high activity polyether polyol is selected from at least two block copolymers of ethylene oxide, propylene oxide, 1, 2-butylene oxide or styrene oxide, and the molecular chain end is-CH 2 OH structure, unsaturation degree less than 0.04mol/kg, number average molecular weight more than 1000 times of the number of hydroxyl groups, primary hydroxyl group content more than 85%.
3. The process for preparing a low unsaturation, high activity polyether polyol according to claim 2, wherein the low unsaturation, high activity polyether polyol has an unsaturation of from 0.01 to 0.035mol/kg and a primary hydroxyl content of greater than 88%.
4. The process for preparing a low unsaturation, high activity polyether polyol according to claim 3, wherein the low unsaturation, high activity polyether polyol has an unsaturation of from 0.01 to 0.03 mole/kg and a primary hydroxyl content of greater than 90%.
5. The method for preparing polyether polyol with low unsaturation degree and high activity according to claim 1, wherein the organophosphorus alkoxide is obtained by reacting an organophosphorus salt of the general formula (3) with an inorganic alcohol base, the organophosphorus salt of the general formula (3) is obtained by reacting phosphorus trichloride with an imine compound of the general formula (2),
wherein Ph is aryl or heteroatom group substituted aryl, n is an integer of 1-3, and A is an anion of inorganic salt.
6. The method for preparing a low unsaturation, high activity polyether polyol according to claim 5, wherein the inorganic alcohol base has the structure of formula (4):
M + RO - (4)
wherein M is + Is an alkali metal ion; r is an alkyl group of 1 to 4 carbon atoms.
7. The method for preparing a low unsaturation, high activity polyether polyol according to claim 5, wherein the anion of the inorganic salt is selected from the group consisting of NO 3 - 、SO 4 2- 、PO 4 2- 、X - 、Cr 2 O 7 2- 、CO 3 2- Or BF 4 - Wherein X is halogen.
8. The process for preparing a low unsaturation, high activity polyether polyol according to claim 7, wherein the anion of the inorganic salt is selected from the group consisting of X - Or BF 4 - Wherein X is halogen.
9. The process for preparing a low unsaturation, high activity polyether polyol of claim 1, wherein the polymerization conditions are: the temperature is 50-160 ℃, the reaction pressure is-0.05-3.0 MPa, and the reaction time is less than 50 hours.
10. The method of preparing a low unsaturation, high activity polyether polyol according to claim 1, wherein the active hydrogen compound is selected from at least one of ethylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, glycerol, trimethylolpropane, diglycerol, trimethylol melamine, pentaerythritol, glucose, sorbitol, dextrose, fructose, or sucrose; the alkylene oxide is selected from at least one of ethylene oxide, propylene oxide, 1, 2-butylene oxide or styrene oxide.
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