CN116874762A - 制备低不饱和度、高分子量聚醚多元醇的方法 - Google Patents
制备低不饱和度、高分子量聚醚多元醇的方法 Download PDFInfo
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- CN116874762A CN116874762A CN202211065075.9A CN202211065075A CN116874762A CN 116874762 A CN116874762 A CN 116874762A CN 202211065075 A CN202211065075 A CN 202211065075A CN 116874762 A CN116874762 A CN 116874762A
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- polyether polyol
- molecular weight
- unsaturation
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- low
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- 229920000570 polyether Polymers 0.000 title claims abstract description 77
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 76
- 229920005862 polyol Polymers 0.000 title claims abstract description 61
- 150000003077 polyols Chemical class 0.000 title claims abstract description 61
- 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 38
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 hydrogen compound Chemical class 0.000 claims abstract description 17
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 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 30
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000002466 imines Chemical class 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 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
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 abstract description 5
- 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
- 230000000694 effects Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 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 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 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
- 238000007670 refining Methods 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
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-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
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 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
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 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
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical group [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003756 stirring Methods 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
- 229920003171 Poly (ethylene oxide) Polymers 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 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
- 239000006260 foam Substances 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-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
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 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
- 239000000126 substance Substances 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
- C08G65/2603—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
- C08G65/2612—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 aromatic or arylaliphatic 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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
本发明涉及一种制备低不饱和度、高分子量聚醚多元醇的方法,主要解决现有技术中生产聚醚多元醇时使用的碱催化剂不能同时满足低不饱和度和高分子量的要求,而同时满足要求的有机催化剂原料成本高的问题。本发明通过采用一种制备低不饱和度、高分子量聚醚多元醇的方法,采用有机磷醇盐作为催化剂,用活性氢化合物和氧化烯烃聚合反应制备低不饱和度、高分子量聚醚多元醇;所述活性氢化合物为含有羟基的有机化合物,选自具有2‑20个碳原子和具有1‑8个羟基的羟基醇类、糖类或其衍生物或具有2‑8个羟基并具有数均分子量为200‑5000的聚醚多元醇的技术方案较好地解决了上述问题,可用于聚醚多元醇的制备中。
Description
技术领域
本发明涉及一种制备低不饱和度、高分子量聚醚多元醇的方法。
背景技术
聚醚多元醇是合成聚氨酯材料的主要原料之一,聚醚多元醇的制备方法很多,主要包括阴离子聚合、阳离子聚合和配位聚合等。阴离子聚合利用无机强碱(例如KOH)为催化剂,无机强碱具有价廉,在聚醚多元醇中容易脱除等优势,在制备低分子量的聚醚多元醇时被广泛的应用于工业生产中;然而,无机强碱容易使环氧丙烷发生异构化,产生末端为不饱和双键的单羟基聚醚,使聚醚多元醇的官能度和相对分子量变小,尤其是在制备高分子量的产物时,其单羟基聚醚的含量很高;例如在制备三官能度相对分子量为5000的聚醚三元醇,其不饱和度达到0.05mol/kg以上;阳离子聚合利用强路易斯酸(例如BF3·乙醚)为催化剂,进行氧化烯烃聚合时会形成二噁烷结构的副产物,对制备的聚氨酯制品的性能有不利的影响,需要利用繁琐的过程除去杂质,工业生产中基本上不采用;双金属氰化络合物催化剂虽然其用于环氧丙烷均聚合和环氧乙烷/环氧丙烷无规共聚合时活性很高,可制得高分子量的聚醚多元醇,但其存在着不能直接采用小分子的多元醇(例如丙三醇)为起始剂,尤其是双金属氰化络合物催化剂在进行环氧乙烷均聚时,会使环氧乙烷发生自聚合反应,生成聚氧化乙烯的副产物,从而影响聚醚多元醇的性能。
高活性聚醚多元醇是指具有伯羟基(—CH2OH)结构的一类品种,使用最广泛的是数均分子量为4500-6000的聚醚三元醇,主要应用在制备高回弹聚氨酯泡沫塑料;高回弹聚氨酯泡沫塑料的制备通常采用二种方法,一种是利用高活性聚醚多元醇同甲苯二异氰酸酯(TDI)反应,这种高活性聚醚多元醇的数均分子量通常在4500-5000之间;另一种是利用高活性聚醚多元醇同二苯基甲烷二异氰酸酯(MDI)反应,这种高活性聚醚多元醇的数均分子量要求更大,通常在6000以上;TDI体系具有工艺比较稳定,制品性能优良,回弹性高等优点,但由于TDI的毒性大,反应活性小,导致生产环境差,固化速度慢,以及低密度泡沫硬度低等问题的存在;MDI体系虽然存在密度大,回弹性低,撕裂性能差一些的缺点,但由于MDI的毒性小,反应活性高,泡沫的雾化性能小,人们一直在寻求合成一种低不饱和度、高分子量、高活性聚醚多元醇,同MDI反应制备密度小、回弹性高、撕裂性能好的泡沫。
中国专利CN104497046B提供了一种有机醇盐及其制备方法,虽然该催化剂用于生产聚醚多元醇时同时具有低不饱和度,高分子量和高活性的优点,但其催化剂原料中采用的胍类物质成本较高,工业生产成本高。
发明内容
本发明所要解决的技术问题是现有技术中生产聚醚多元醇时使用的碱催化剂不能同时满足低不饱和度和高分子量的要求,而同时满足要求的有机催化剂原料成本高的问题,提供一种新的制备低不饱和度、高分子量聚醚多元醇的方法,该方法用于聚醚多元醇的制备中,具有同时满足低不饱和度和高分子量的优点,且催化剂原料成本低。
为解决上述问题,本发明采用的技术方案如下:一种制备低不饱和度、高分子量聚醚多元醇的方法,采用有机磷醇盐作为催化剂,用活性氢化合物和氧化烯烃聚合反应制备低不饱和度、高分子量的聚醚多元醇;所述的有机磷醇盐结构通式(1)为:
其中,Ph为芳基或杂原子基团取代芳基,R为1-4个碳原子的烷基;所述活性氢化合物为含有羟基的有机化合物,选自具有2-20个碳原子和具有1-8个羟基的羟基醇类、糖类或其衍生物或具有2-8个羟基且数均分子量为200-5000的聚醚多元醇。
上述技术方案中,优选地,所述氧化烯烃选自环氧乙烷、环氧丙烷、1、2-环氧丁烷或氧化苯乙烯中的至少一种;聚醚多元醇选自环氧乙烷、环氧丙烷、1、2-环氧丁烷或氧化苯乙烯中的至少两种的嵌段共聚物,分子链末端为-CH2OH结构,不饱和度小于0.04mol/kg,数均分子量是其羟基个数的1000倍以上,伯羟基含量大于85%。
上述技术方案中,更优选地,所述聚醚多元醇的不饱和度为0.01-0.035mol/kg,伯羟基含量大于88%。
上述技术方案中,最优选地,所述聚醚多元醇的不饱和度为0.01-0.03mol/kg,伯羟基含量大于90%。
上述技术方案中,优选地,所述有机磷醇盐是由通式(3)的有机磷盐与无机醇碱反应得到,通式(3)的有机磷盐由五卤化磷与通式(2)的亚胺类化合物反应得到,
其中,Ph为芳基或杂原子基团取代芳基,n为1-3的整数,A为无机盐的阴离子。
上述技术方案中,更优选地,所述的无机醇碱具有通式(4)的结构:
M+RO- (4)
其中,M+为碱金属离子;R为1-4个碳原子的烷基。
上述技术方案中,更优选地,所述的无机盐的阴离子选自NO3 -、SO4 2-、PO4 2-、X-、Cr2O7 2-、CO3 2-或BF4 -,其中X为卤素。
上述技术方案中,最优选地,所述的无机盐的阴离子选自X-或BF4-,其中X为卤素。
上述技术方案中,优选地,所述聚合反应的条件为:温度为50-160℃,反应压力为-0.05-3.0MPa,反应时间小于50小时。
上述技术方案中,优选地,活性氢化合物选自乙二醇、二甘醇、二丙二醇、1、3-丙二醇、1、2-丙二醇、1、3-丁二醇、1、4-丁二醇、甘油、三羟甲基丙烷、二甘油、三羟甲基密胺、季戊四醇、葡萄糖、山梨糖醇、右旋糖、果糖或蔗糖中的至少一种;氧化烯烃为环氧乙烷、环氧丙烷、1、2-环氧丁烷或氧化苯乙烯中的至少一种。
本发明所述聚醚多元醇的实际官能度高,且随分子量的增加下降较少。
具体实施过程如下:
首先合成用结构通式(1)表示的有机磷醇盐,Ph可以选用相同或不同的芳基或杂原子取代芳基,具体地说Ph可以选用苯基、对氯苯基、对溴苯基、对碘苯基或对硝基苯基,最优选的是苯基,R为1-4个碳原子的烷基,优选甲基。
将具有通式为(2)的亚胺类化合物在芳烃溶剂存在下与五氯化磷反应,生成结构通式为(3)的有机磷盐,这类有机磷盐选自以下化合物,例如:四(二苯甲酮亚胺基)氯化鏻、四[二(4-氯)苯甲酮亚胺基]氯化鏻、四[二(4-溴)苯甲酮亚胺基]氯化鏻、四[二(4-碘)苯甲酮亚胺基]氯化鏻、四[二(4-硝基)苯甲酮亚胺基]氯化鏻等;也可以将这些盐的阴离子转化为NO3 -、SO4 2-、PO4 2-、Cr2O7 2-、CO3 2-或BF4 -;再将有机磷盐用选自碱金属或碱土金属的无机醇碱反应,生成通式为(1)的有机磷醇盐催化剂;无机醇碱选自甲醇钾、甲醇钠、乙醇钾、乙醇钾、丙醇钾、丙醇钠、丁醇钾、丁醇钠等;有机磷盐是由通式为(2)的亚胺类化合物和五卤化磷反应而制得;无机醇碱具有通式(4)的结构,其中M+为碱金属或碱土金属离子;R为1-4碳原子的烷基。
聚醚多元醇的制备采用有机磷醇盐为催化剂,将含活性氢化合物和氧化烯烃在一定温度和压力下聚合反应而制得;在本发明中含活性氢化合物是指含有羟基的有机化合物,选用:具有2-20个碳原子和1-8个羟基的羟基醇类、糖类或其衍生物,例如:乙二醇,二甘醇,二丙二醇,1、3-丙二醇,1、2-丙二醇,1、3-丁二醇,1、4-丁二醇,甘油,三羟甲基丙烷,二甘油,三羟甲基密胺,季戊四醇,葡萄糖,山梨糖醇,右旋糖,果糖,蔗糖等,具有2-8羟基数的分子量为200-5000的聚醚多元醇;在本发明中氧化烯烃包括环氧乙烷,环氧丙烷,1、2-环氧丁烷和氧化苯乙烯或它们的混合物,氧化烯烃分段加入,后期必须是环氧乙烷。
在本发明中,有机磷醇盐的量没有特别的限定,但用量常在1×10-6—5×10-3g/mol氧化烯烃,优选5×10-5—2×10-3g/mol氧化烯烃。
在本发明中,聚合反应的温度选择在50-160℃,优选在70-130℃,更优选在80-100℃范围内;聚合反应压力选择在-0.05-3.0MPa,优选在0.01-1MPa,更优选在0.05-0.5MPa范围内;聚合反应时间选择在50小时以内,优选在1-30小时,更优选在5-24小时。
本发明中制备的聚醚多元醇可以采用常用的精制方法脱除有机磷醇盐催化剂,例如吸附法或酸型离子交换树脂处理之后使用。
本发明中由于采用了一种新型的有机磷醇盐作为制备聚醚多元醇的催化剂,惊奇的发现使用该有机磷醇盐催化剂可在较低的温度下制得聚醚多元醇,并具有低不饱和度和高分子量的特点,且合成催化剂所用的原料为亚胺类化合物,成本低于胍类催化剂,取得了较好的技术效果。
下面通过实施例对本发明作进一步的阐述,但不仅限于本实施例。
具体实施方式
【实施例1】
在装有搅拌器、温度计、滴液漏斗的3000ml三口烧瓶中加入208.2g五氯化磷和1000ml邻二氯苯,在氮气保护下,慢慢滴加1450g二苯甲酮亚胺,控制反应温度在90℃,滴加结束后,慢慢冷却至常温,在常温下搅拌4小时,过滤除去沉淀物,在得到的溶液中加入81g甲醇钠和400ml甲醇,在50℃下反应5小时,减压蒸馏除去甲醇后,过滤除去沉淀物,得催化剂A,质量为626.2g。
【实施例2】
在装有搅拌器、温度计、滴液漏斗的3000ml三口烧瓶中加入104.1g五氯化磷和1000ml邻二氯苯,在氮气保护下,慢慢滴加724.8g二苯甲酮亚胺,控制反应温度在90℃,滴加结束后,慢慢冷却至常温,在常温下搅拌2.5小时,过滤除去沉淀物,将得到的溶液减压脱除邻二氯苯后加入10%wtNaBF4的水溶液824g,在45℃下反应2.5小时,降温至10℃以下,得到白色固体,将得到的固体加入52.6g甲醇钾和200ml甲醇,在常温下反应5小时,离心分离固体后,在50℃减压蒸馏除去甲醇后,得催化剂B,质量为328.8g。
【实施例3】
按照实施例2所述的条件和步骤,用10%wt Na2CO3的水溶液795g代替NaBF4,得催化剂C,质量为320.9g。
【实施例4】
按照实施例2所述的条件和步骤,用二(4-溴)苯甲酮亚胺替代二苯甲酮亚胺,得催化剂D,质量为576.2g。
【实施例5】
按照实施例2所述的条件和步骤,用二(4-硝基)苯甲酮亚胺替代二苯甲酮亚胺,得催化剂E,质量为477.1g。
【实施例6】
在装有温度计、压力表和搅拌器的2L高压反应釜中加入7.5g催化剂A和120g700分子量三官的粗聚醚多元醇,经抽真空和氮气置换除去氧气,当氧气含量小于150ppm以后,抽真空至反应釜的压力降至为-0.09MPa,当温度升至95℃时,慢慢加入环氧丙烷1130g,控制反应压力<0.4MPa,待环氧丙烷加完以后,继续搅拌至反应釜的压力不再发生变化,慢慢加入环氧乙烷250g,反应结束后得淡黄色粗聚醚三元醇1460g。将得到的粗聚醚三元醇通过磷酸中和,脱水和硅酸镁吸附后得精制的聚醚三元醇。经分析测定,其羟值为22.5mgKOH/g,不饱和度为0.027mol/Kg,伯羟基含量为90.6%,理论官能度为3.00,实际官能度为2.64。
【实施例7】
在装有温度计、压力表和搅拌器的2L高压反应釜中加入6g催化剂B和120g700分子量三官的粗聚醚多元醇,经抽真空和氮气置换除去氧气后,当氧气含量小于150ppm以后,在95℃的温度下慢慢加入环氧丙烷1130g,控制反应压力<0.4Mpa。待环氧丙烷反应结束后,再慢慢加入250g环氧乙烷,反应结束后得淡黄色的粗聚醚三元醇1482.0g,精制后其羟值为22.6mgKOH/g,不饱和度为0.025mol/Kg,伯羟基含量为91.0%,理论官能度为3.00,实际官能度为2.67。
【实施例8】
按照实施例7所述的条件和步骤,用催化剂C替代催化剂B。得到精制的聚醚三元醇,其羟值为22.9mgKOH/g,不饱和度为0.028mol/Kg,伯羟基含量为88.7%,理论官能度为3.00,实际官能度为2.64。
【实施例9】
按照实施例7所述的条件和步骤,用6g催化剂D替代催化剂B。得到精制的聚醚三元醇,其羟值为22.8mgKOH/g,不饱和度为0.026mol/Kg,伯羟基含量为89.3%,理论官能度为3.00,实际官能度为2.60。
【实施例10】
按照实施例7所述的条件和步骤,用6g催化剂E替代催化剂B。得到精制的聚醚三元醇,其羟值为23.0mgKOH/g,不饱和度为0.027mol/Kg,伯羟基含量为88.0%,理论官能度为3.00,实际官能度为2.58。
【实施例11】
在装有温度计,压力表和搅拌器的2L高压反应釜中加入4.5g催化剂B和120g700分子量三官的粗聚醚多元醇,经抽真空和氮气置换除去氧气,当氧气含量小于150ppm以后,抽真空至反应釜的压力降至为0.09MPa,当温度升至95℃时,慢慢加入环氧丙烷1130g,控制反应压力小于0.4MPa,待环氧丙烷加完以后,再慢慢加入250g环氧乙烷,反应结束后得淡黄色的粗聚醚三元醇1475g,精制后其羟值为23.1mgKOH/g,不饱和度为0.028mol/kg,伯羟基含量为91.1%,理论官能度为3.00,实际官能度为2.81。
【实施例12】
按照实施例11所述的条件和步骤,用102g600分子量的三官粗聚醚多元醇代替120g700分子量三官的粗聚醚多元醇,反应结束后得到精制聚醚三元醇,其羟值为25.8mgKOH/g,不饱和度为0.027mol/kg,伯羟基含量为91.3%,理论官能度为3.00,实际官能度为2.68。
【实施例13】
在装有温度计,压力表和搅拌器的2L高压反应釜中加入6g催化剂B和120g700分子量三官的粗聚醚多元醇,经抽真空和氮气置换除去氧气后,当氧气含量小于150ppm以后,在125℃的温度下,慢慢加入环氧丙烷1130g,控制反应压力小于0.4MPa,待环氧丙烷反应结束后,再慢慢加入250g环氧乙烷,反应结束后得淡黄色的粗聚醚三元醇1492g,精制后其羟值为23.4mgKOH/g,不饱和度为0.029mol/kg,伯羟基含量为89.8%,理论官能度为3.00,实际官能度为2.63。
【实施例14】
在装有温度计,压力表和搅拌器的2L高压反应釜中加入3g催化剂B和120g700分子量三官的粗聚醚多元醇,经抽真空和氮气置换除去氧气后,当氧气含量小于150ppm以后,在95℃的温度下,慢慢加入环氧丙烷739g,控制反应压力小于0.4MPa,待环氧丙烷反应结束后,再慢慢加入149g环氧乙烷,反应结束后得淡黄色的粗聚醚三元醇998g,精制后其羟值为33.5mgKOH/g,不饱和度为0.017mol/kg,伯羟基含量为84.5%,理论官能度为3.00,实际官能度为2.58。
【比较例1】
在装有温度计、压力表和搅拌器的2L高压反应釜中加入4.5gKOH和120g700分子量三官的粗聚醚多元醇,经抽真空和氮气置换除去氧气,当氧气含量小于150ppm以后,将温度升至120℃抽真空脱水1h,慢慢加入环氧丙烷1130g,控制反应压力小于0.4MPa,待环氧丙烷加完以后,再慢慢加入250g环氧乙烷,反应结束后得淡黄色的粗聚醚三元醇1389g,精制后其羟值为25.0mgKOH/g,不饱和度为0.088mol/kg,伯羟基含量为87.2%,理论官能度为3.00,实际官能度为2.84。
【比较例2】
按照实施例14所述的条件和步骤,采用3gKOH替代催化剂B,在120℃抽真空脱水1小时,得到精制的聚醚三元醇,其羟值为32.6mgKOH/g,不饱和度为0.098mol/kg,伯羟基含量为76.4%,理论官能度为3.00,实际官能度为2.24。
Claims (10)
1.一种制备低不饱和度、高分子量聚醚多元醇的方法,采用有机磷醇盐作为催化剂,用活性氢化合物和氧化烯烃聚合反应制备低不饱和度、高分子量的聚醚多元醇;所述的有机磷醇盐的结构通式(1)如下:
其中,Ph为芳基或杂原子基团取代芳基,R为1-4个碳原子的烷基;所述活性氢化合物为含有羟基的有机化合物,选自具有2-20个碳原子和具有1-8个羟基的羟基醇类、糖类或其衍生物或具有2-8个羟基并具有数均分子量为200-5000的聚醚多元醇。
2.根据权利要求1所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述氧化烯烃选自环氧乙烷、环氧丙烷、1、2-环氧丁烷或氧化苯乙烯中的至少一种;聚醚多元醇选自环氧乙烷、环氧丙烷、1、2-环氧丁烷或氧化苯乙烯中的至少两种的嵌段共聚物,分子链末端为-CH2OH结构,不饱和度小于0.04mol/kg,数均分子量是其羟基个数的1000倍以上,伯羟基含量大于85%。
3.根据权利要求2所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述聚醚多元醇的伯羟基含量大于88%,不饱和度为0.01-0.035mol/kg。
4.根据权利要求3所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述聚醚多元醇的伯羟基含量大于90%,不饱和度为0.01-0.03mol/kg。
5.根据权利要求1所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述有机磷醇盐是由通式(3)的有机磷盐与无机醇碱反应得到,通式(3)的有机磷盐由五卤化磷与通式(2)的亚胺类化合物反应得到,
其中,Ph为芳基或杂原子基团取代芳基,n为1-3的整数,A为无机盐的阴离子。
6.根据权利要求5所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述的无机醇碱具有通式(4)的结构:
M+RO- (4)
其中,M+为碱金属离子;R为1-4个碳原子的烷基。
7.根据权利要求5所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述的无机盐的阴离子选自NO3 -、SO4 2-、PO4 2-、X-、Cr2O7 2-、CO3 2-或BF4 -,其中X为卤素。
8.根据权利要求7所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述的无机盐的阴离子选自X-或BF4 -,其中X为卤素。
9.根据权利要求1所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述的聚合反应的条件为:温度为50-160℃,反应压力为-0.05-3.0MPa,反应时间小于50小时。
10.根据权利要求1所述制备低不饱和度、高分子量聚醚多元醇的方法,其特征在于,所述的活性氢化合物选自乙二醇、二甘醇、二丙二醇、1、3-丙二醇、1、2-丙二醇、1、3-丁二醇、1、4-丁二醇、甘油、三羟甲基丙烷、二甘油、三羟甲基密胺、季戊四醇、葡萄糖、山梨糖醇、右旋糖、果糖或蔗糖中的至少一种;氧化烯烃选自环氧乙烷、环氧丙烷、1、2-环氧丁烷或氧化苯乙烯中的至少一种。
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