CN100398580C - 制备聚醚醇的方法 - Google Patents
制备聚醚醇的方法 Download PDFInfo
- Publication number
- CN100398580C CN100398580C CNB2004800232060A CN200480023206A CN100398580C CN 100398580 C CN100398580 C CN 100398580C CN B2004800232060 A CNB2004800232060 A CN B2004800232060A CN 200480023206 A CN200480023206 A CN 200480023206A CN 100398580 C CN100398580 C CN 100398580C
- Authority
- CN
- China
- Prior art keywords
- alkylene oxide
- aethoxy sklerol
- reaction
- starter substance
- solvent
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 229920000570 polyether Polymers 0.000 title abstract description 7
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 6
- 150000001298 alcohols Chemical class 0.000 title abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000126 substance Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims description 69
- 239000007858 starting material Substances 0.000 claims description 34
- 238000005844 autocatalytic reaction Methods 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 19
- -1 oxybutylene Chemical group 0.000 claims description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000007259 addition reaction Methods 0.000 claims description 7
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IXQXHNUAENXGAH-UHFFFAOYSA-N 1-(dimethylamino)-1-ethoxyethanol Chemical compound CCOC(C)(O)N(C)C IXQXHNUAENXGAH-UHFFFAOYSA-N 0.000 claims description 2
- ADQQGJLCEXHTRW-UHFFFAOYSA-N 1-(dimethylamino)hexan-1-ol Chemical compound CCCCCC(O)N(C)C ADQQGJLCEXHTRW-UHFFFAOYSA-N 0.000 claims description 2
- WCDFMPVITAWTGR-UHFFFAOYSA-N 1-imidazol-1-ylpropan-2-ol Chemical class CC(O)CN1C=CN=C1 WCDFMPVITAWTGR-UHFFFAOYSA-N 0.000 claims description 2
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical class NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 abstract description 9
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 229920001228 polyisocyanate Polymers 0.000 description 11
- 239000005056 polyisocyanate Substances 0.000 description 11
- 229920005830 Polyurethane Foam Polymers 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 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 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 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 description 2
- 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 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 2
- BSRRYOGYBQJAFP-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluorobutane Chemical compound CC(F)C(F)(F)C(F)(F)F BSRRYOGYBQJAFP-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical compound N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 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 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 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 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- FGFWCOVNCKWNLU-UHFFFAOYSA-N oxalic acid;tin Chemical compound [Sn].OC(=O)C(O)=O FGFWCOVNCKWNLU-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 102220058219 rs730881936 Human genes 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000004711 α-olefin 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
- 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
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Abstract
本发明涉及一种通过使H官能起始剂物质与烯化氧反应而制备自催化聚醚醇的方法,其中H官能起始剂物质含有含至少一个在氨基甲酸酯反应中呈催化活性的氨基,尤其是叔氨基和至少一个与烯化氧反应的基团,尤其是伯和/或仲氨基和/或羟基的化合物。该方法包括下列步骤:a)将起始剂物质溶于溶剂中,和b)使该溶液与烯化氧反应。
Description
长期以来聚醚醇是已知的且广泛描述于文献中。它们尤其通过与多异氰酸酯反应而进一步加工得到聚氨酯。它们通常通过将烯化氧加成到含有活性氢原子的低分子量起始剂物质上而制备。
特殊类型的聚醚醇通过使用含有氨基的化合物作为起始剂物质制备的那些而形成。因为叔氨基催化聚氨酯反应,因此这类聚醚醇同时用作聚氨酯的形成组分和催化剂。与常规的低分子量胺催化剂相比,通常也称为自催化聚醚醇的该类聚醚醇的优点在于它们不能从泡沫中迁移出来。胺从泡沫中迁移出来导致令人不愉快的气味且因此是不可取的。现有技术中已知一些这类自催化聚醚醇。
作为自催化聚醚醇的起始剂物质,可以使用具有伯、仲和/或叔氨基的化合物。在与烯化氧的反应中,伯和仲氨基转化成叔氨基。其起始剂物质最初含有叔氨基的自催化聚醚醇的催化活性通常高于其叔氨基仅通过伯或仲氨基与烯化氧的反应而形成的聚醚醇的催化活性。
DD 235878描述了通过将烯化氧加成到具有低叔氨基含量的脂族四胺上而制备的自催化聚醚醇。根据终产物的所需性质,胺可以立即与全部量的烯化氧反应或依次与多个部分量的烯化氧反应。
WO 01/58976、WO 02/22702、WO 03/016372和WO 03/29320描述了许多通过将烯化氧加成到各种胺上而制备的自催化聚醚醇。这些自催化聚醚醇优选与其他多元醇结合而与异氰酸酯反应以得到聚氨酯。它们通过将烯化氧加成到用作起始剂物质的胺上而由常规方法制备。
使用自催化聚醚醇能够显著抑制用作催化剂的胺所引起的不希望的气味。然而,根据现有技术制备的聚醚醇仍然总是含有可能导致聚氨酯气味问题的副产物。此外,已经发现使用常规自催化聚醚醇生产的聚氨酯的耐老化性质并不令人满意。
本发明的目的是开发不含副产物、气味轻且制备简单的自催化聚醚醇。
我们发现该目的通过在与烯化氧反应之前将用作起始剂物质的胺溶于溶剂中并使它们与烯化氧在溶液中反应而实现。
本发明因此提供了一种通过使H官能起始剂物质与烯化氧反应而制备自催化聚醚醇的方法,其中H官能起始剂物质含有至少一个在氨基甲酸酯反应中呈催化活性的氨基,尤其是叔氨基和至少一个对烯化氧呈反应性的基团,尤其是伯和/或仲氨基和/或羟基,该方法包括:
a)将起始剂物质溶于溶剂中,和
b)使该溶液与烯化氧反应。
本发明进一步提供了由该方法制备的聚醚醇。
此外,本发明提供了一种通过使多异氰酸酯与具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物反应而生产聚氨酯的方法,其中将至少一种可以通过本发明方法制备的自催化聚醚醇用作具有至少两个对氨基甲酸酯基团呈反应性的氢原子的化合物。
作为溶剂,可以使用任何有机溶剂。在本发明方法的一个实施方案中,将对烯化氧呈化学惰性的有机溶剂用作溶剂。
优选这些惰性有机溶剂的沸点低于起始剂物质与烯化氧的反应中的反应温度。具体而言,该沸点为至少100℃。该有机溶剂的实例为甲苯、一氯苯、二甘醇二甲基醚和三甘醇二甲基醚。
起始剂物质与溶剂的重量比优选为1∶20至20∶1,特别优选1∶1至1∶10,尤其是1∶1至1∶5。
在该实施方案中,应当在与烯化氧反应之后除去溶剂,因为溶剂可能在聚醚醇形成聚氨酯的反应中引起问题并且其本身可能导致不希望的气味。
在本发明方法的优选实施方案中,将聚醚醇用作溶剂。作为聚醚醇优选使用已知且常用于聚氨酯生产的产物。优选的聚醚醇具有的官能度为2-8且羟基数为20-1200mg KOH/g。对于用作溶剂的聚醚醇的选择优选由自催化聚醚醇的所需应用领域决定。因此,对于用于生产硬质泡沫的自催化聚醚醇的情况,优选使用低分子量和高官能度的聚醚醇。该类产物优选具有3-8的官能度和200-1200mg KOH/g的羟基数。该类产物通常是已知的。它们优选通过将低级烯化氧,尤其是氧化乙烯和/或氧化丙烯加成到含有醇和/或胺基团的起始剂物质例如甘油、三羟甲基丙烷或糖类如蔗糖或山梨糖醇上而制备。对于用于生产软质泡沫的自催化聚醚醇的情况,优选使用羟基数为20-200mg KOH/g,尤其是20-100mg KOH/g的双官能至三官能聚醚醇。该类产物通常也是已知的。它们优选通过将低级烯化氧,尤其是氧化乙烯和/或氧化丙烯加成到双官能和三官能醇如甘油、三羟甲基丙烷、乙二醇及其同系物以及丙二醇及其同系物上而制备。
在本发明方法的该实施方案中,令人意外的是烯化氧大为选择性地加成到含有至少一个伯、仲或叔氨基的H官能起始剂物质上。
这首先导致自催化聚醚醇具有窄分子量分布。此外,显著抑制了在将烯化氧加成到含有胺基团的起始剂物质上的过程中的次级反应。
当将聚醚醇用作溶剂时,本发明方法的各种实施方案是可能的。
在一个实施方案中,使用进行了完全后处理和提纯的聚醚醇。此时,可以仅利用起始剂物质的催化性质而不加入其他催化剂以进行烯化氧在含有胺基团的起始剂物质上的加成。该实施方案的优点是在烯化氧的加成反应之后不必进行聚醚醇的后处理。这里的缺点是加成反应的反应速率低。该反应速率可以通过加入碱性催化剂而提高,但此时通常需要随后除去碱性催化剂。
在本发明方法的另一个优选实施方案中,将仍含有碱性催化剂的未提纯聚醚醇用作溶剂。碱性催化剂是常用于制备聚醚醇的碱催化剂之一,例如氢氧化铯、氢氧化钠和尤其是氢氧化钾。基于未提纯聚醚醇的重量,该催化剂的存在量通常为0.1-3.0重量%。
在烯化氧的加成以及一段通常紧随其后以使烯化氧完全反应的后反应时间之后,通过中和碱性催化剂并除去所得盐而以常规方式后处理所得的自催化聚醚醇。
起始剂物质与聚醚醇的重量比优选为1∶20至20∶1,特别优选1∶1至1∶10,尤其是1∶1至1∶5。
作为含有胺基团的起始剂物质,如上所述可以使用所有催化氨基甲酸酯反应的胺。优选使用具有至少一个叔氨基,尤其是二烷基氨基以及至少一个可以与烯化氧反应的官能基团的化合物。可以与烯化氧反应的官能基团可以是任何H官能基团。它们优选为羟基或伯和/或仲氨基。
作含有胺基团的起始剂物质,原则上可以使用所有例如WO 01/58976、WO 02/22702、WO 03/016372和WO 03/29320中所述的化合物。
优选的含有胺基团的起始剂物质是具有至少一个叔氨基和H官能基团的脂族胺。
含有胺基团的起始剂物质优选选自二甲氨基乙胺、二甲氨基丙胺、二乙氨基乙胺、二乙氨基丙胺、N-(3-二甲氨基丙基)-N,N-二异丙醇胺、二甲基乙醇胺、N,N-二甲氨基乙基·N’-甲基-N’-羟乙基氨基乙基醚、N,N-二(3-二甲氨基丙基)氨基-2-丙醇胺、二(N,N-二甲基-3-氨基丙基)胺、N,N-二甲氨基乙氧基乙醇、N-(3-氨基丙基)咪唑、N-(2-二甲氨基乙基)-N-甲基乙醇胺、N-(2-羟丙基)咪唑、二甲氨基己醇以及至少两种所述化合物的混合物。
本发明方法的进行优选使平均1-8,优选1-6,尤其是2-4分子的烯化氧加成到含有胺基团的起始剂物质的每个活性氢原子上。
起始剂物质与烯化氧的反应在0.1-1.0MPa的常规压力和80-140℃的常规温度下进行。引入烯化氧之后通常进行后反应阶段以使烯化氧完全反应。胺的催化活性通常足以引起烯化氧的加成反应。必要的话,可以加入另外的催化剂。这些催化剂尤其是碱性催化剂,优选碱催化剂。
在烯化氧的加成和后反应阶段之后,必要的话从聚醚醇中除去催化剂。
由本发明方法制备的自催化聚醚醇可以单独反应或优选与具有至少两个对异氰酸酯基团呈反应性的氢原子的其他化合物结合反应以得到聚氨酯。
作为可以与本发明的自催化聚醚醇一起使用的具有至少两个活性氢原子的化合物,尤其可以使用聚酯醇和优选聚醚醇,其官能度为2-8,尤其是2-6,优选2-4且平均分子量为400-10000g/mol,优选1000-8000g/mol。基于所有具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物的重量,本发明自催化聚醚醇在具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物中的含量优选为0.1-20重量%,特别优选0.5-10重量%。
聚醚醇可以通常通过烯化氧,尤其是氧化乙烯和/或氧化丙烯在H官能起始剂物质上的催化加成,或通过四氢呋喃的缩合而由已知方法制备。所用H官能起始剂物质尤其是多官能醇和/或胺。优选使用水,二元醇如乙二醇、丙二醇或丁二醇,三元醇如甘油或三羟甲基丙烷,还有更高官能度的醇如季戊四醇,糖醇如蔗糖、葡萄糖或山梨糖醇。优选的胺是具有至多10个碳原子的脂族胺如乙二胺、二亚乙基三胺、丙二胺,以及氨基醇如乙醇胺或二乙醇胺。作为烯化氧,优选使用氧化乙烯和/或氧化丙烯,其中对于用于生产软质聚氨酯泡沫的聚醚醇的情况,氧化乙烯嵌段通常加成在链末端。用于烯化氧的加成反应中的催化剂尤其是碱性化合物,在这里氢氧化钾具有最大的工业重要性。当希望不饱和成分在聚醚醇中的含量低时,还可以使用多金属氰化物(已知为DMC催化剂)作为催化剂。
对于特殊应用,尤其对于增加软质聚氨酯泡沫的硬度,还可以使用聚合物改性的多元醇。该类多元醇例如可以通过烯属不饱和单体(优选苯乙烯和/或丙烯腈)在聚醚醇中原位聚合而制备。聚合物改性的聚醚醇还包括含有聚脲分散体的聚醚醇,其优选通过使胺与异氰酸酯在多元醇中反应而制备。
为了生产软质泡沫和整体泡沫,尤其使用双官能和/或三官能的聚醚醇。为了生产硬质泡沫,尤其使用通过将烯化氧加成到四官能或更高官能度的起始剂如糖醇或芳族胺上而制备的聚醚醇。
具有至少两个活性氢原子的化合物还包括可以同时使用的扩链剂和交联剂。作为扩链剂和交联剂,优选使用分子量低于400g/mol,尤其为60-150g/mol的2和3官能醇。实例是乙二醇、丙二醇、二甘醇、1,4-丁二醇、甘油和三羟甲基丙烷。作为交联剂,还可以使用二胺。若使用扩链剂和交联剂,则基于具有至少两个活性氢原子的化合物的重量,它们的优选用量为至多5重量%。
作为多异氰酸酯,可以使用常规且已知的芳族二异氰酸酯和多异氰酸酯,它们单独使用或以相互之间的任何混合物使用。芳族二异氰酸酯或多异氰酸酯的实例是甲苯-2,4-二异氰酸酯(2,4-TDI),甲苯-2,6-二异氰酸酯(2,6-TDI),二苯基甲烷-2,4’-二异氰酸酯(2,4’-MDI),二苯基甲烷-4,4’-二异氰酸酯(4,4’-MDI),通过苯胺和甲醛的缩合并随后光气化而制备的多苯基多亚甲基多异氰酸酯(聚合MDI),对亚苯基二异氰酸酯,甲苯胺二异氰酸酯,亚二甲苯基二异氰酸酯和奈-1,5-二异氰酸酯(NDI)。
与这些单体异氰酸酯或其混合物一起或代替这些单体异氰酸酯或其混合物,可以使用并且确实优选使用由其制备的低聚异氰酸酯或多异氰酸酯(已知为预聚物),尤其是基于TDI和MDI的预聚物。这些低聚异氰酸酯或多异氰酸酯可以通过借助氨基甲酸酯、脲基甲酸酯、脲、缩二脲、缩脲二酮(uretdione)、酰胺、异氰脲酸酯、碳二亚胺、缩脲酮亚胺(uretonimine)、噁二嗪三酮或亚氨基噁二嗪二酮结构的连接而由上述二异氰酸酯或多异氰酸酯或其混合物和合适的话一元醇或多醇制备。优选使用衍生于TDI或MDI和合适的话一元醇或多醇并且具有氨基甲酸酯、脲基甲酸酯、碳二亚胺、缩脲酮亚胺、缩二脲或异氰酸酯基团的聚合物。
为了生产聚氨酯,可以同时使用其他原料,尤其是其他催化剂、发泡剂和辅助剂和/或添加剂,对其可以给出如下详情:
作为生产本发明聚氨酯泡沫的催化剂,可以使用常规且已知的聚氨酯形成催化剂,例如有机锡化合物如二乙酸锡、二辛酸锡、二月桂酸二烷基锡和/或强碱性胺如三乙胺、五甲基二亚乙基三胺、二(二甲氨基乙基)醚、咪唑或优选三亚乙基二胺,它们与自催化聚醚醇结合。催化剂用量优选为0.01-5重量%,优选0.05-2重量%。
作为生产聚氨酯泡沫的发泡剂,优选使用与异氰酸酯基团反应以释放二氧化碳的水。与水一起或代替水,还可以使用物理作用的发泡剂,例如二氧化碳,烃类如正戊烷、异戊烷或环戊烷、环己烷,或卤代烃类如四氟乙烷、五氟丙烷、七氟丙烷、五氟丁烷、六氟丁烷或二氯一氟乙烷。物理发泡剂的量优选为1-15重量%,尤其是1-10重量%,且水的量优选为0.5-10重量%,尤其是1-5重量。
所用辅助剂和/或添加剂例如为表面活性物质、泡沫稳定剂、泡孔调节剂、外部和内部脱模剂、填料、阻燃剂、颜料、水解抑制剂以及抑制真菌和细菌的物质。
在聚氨酯泡沫的工业生产中,通常在反应之前将具有至少两个活性氢原子的化合物和其他原料如辅助剂和/或添加剂结合以形成多元醇组分。
有关所用原料的其他信息例如可以在Kunststoffhandbuch,第7卷,Polyurethane(聚氨酯),Günter Oertel编辑,Carl-Hanser-Verlag,Munich,第3版,1993中找到。
为了生产本发明的聚氨酯,使有机多异氰酸酯与具有至少两个活性氢原子的化合物在通常混合在一起作为多元醇组分的上述发泡剂、催化剂和辅助剂和/或添加剂存在下反应。
在聚氨酯的生产中,将异氰酸酯和多元醇组分混合在一起,其用量使异氰酸酯基团与活性氢原子总和的当量比为0.6∶1至1∶1.4,优选0.7∶1至1∶1.20。
本发明制备自催化聚醚醇的方法使副产物的形成显著降低。这例如反映在更低的聚醚醇色数上。在这里色数随着含胺基团的起始剂物质在溶剂中的稀释度增加而降低。此外,由本发明方法制备的聚醚醇的固有气味显著低于由常规方法制备的自催化聚醚醇的固有气味,甚至在标准化条件下,即当这些常规催化聚醚醇已经通过加入聚醚醇而稀释到相同的胺含量时也是如此。
在其制备中使用聚醚醇作为溶剂的自催化聚醚醇除了它们可以简单方式制备以外的另一显著优点是原料管理和后勤得以简化,因为在该实施方案中用作聚氨酯本身的形成组分的聚醚醇具有催化性质并因此不必使用另外的催化剂。该制备方法还导致自催化聚醚醇在用作溶剂的聚醚醇中的最佳分布。
由下列实施例说明本发明。
实施例1a
将102.2g(1mol)N,N-二甲氨基丙胺溶于100g氯苯中并与0.2重量%固体氢氧化钾混合。然后引入348.5g(6mol)氧化丙烯。在引入氧化丙烯的过程中,温度为95-105℃,而在后反应过程中温度为95℃。将反应混合物在约98℃下真空汽提1小时。借助氮气破坏真空。通过在室温下加入在2重量%水中的并随后在90℃下搅拌1小时而除去催化剂。然后过滤反应混合物并通过蒸馏除去氯苯。
实施例1b-1f
使用类似于实施例1a的方法,将102.2g(1mol)N,N-二甲氨基丙胺溶于300g、500g和1000g氯苯(实施例1b、1c、1d)或100g和500g二甘醇二甲醚(实施例1e和1f)中并与0.2重量%氢氧化钾混合。然后引入348.5g(6mol)氧化丙烯。如实施例1a所述使用/水2%进行进一步后处理。
通过GC分析来自反应1a-1f的产物。结果表明在胺起始剂的丙氧基化中增加稀释度,即不太剧烈的反应条件,能够显著降低副产物的量。这伴随着产物颜色的变化。起始化合物和溶剂的比例为1∶1所得的样品为棕色,而使用1∶5和1∶10的混合比生产的产物分别为黄色和仅为略黄。
样品 | 目标产物(重量%) |
1a | 12.4 |
1b | 22.6 |
1c | 29.8 |
1d | 37.3 |
1e | 13.9 |
1f | 25.7 |
对比例2
将614g(2.5mol)N,N-二(3-二甲氨基丙基)氨基-2-丙醇胺与0.2重量%氢氧化钾混合。然后在95-105℃下经100分钟计量加入291g(5mol)氧化丙烯。在95℃下进行后反应。然后通过类似于实施例1a的方法使用/水2%后处理反应混合物。
实施例3(根据本发明)
将540g总碱度为0.29%、羟基数为26.5mg KOH/g以及官能度为2.7的衍生于甘油、氧化丙烯和氧化乙烯的碱性聚醚醇与245g(1mol)N,N-二(3-二甲氨基丙基)氨基-2-丙醇胺混合并使该混合物与116g(2mol)氧化丙烯反应而不进行另外的催化。在95℃下进行后反应。然后通过类似于实施例1a的方法使用/水2%后处理反应混合物。
实施例4
将608g总碱度为0.38%、羟基数为25mg KOH/g以及官能度为2.7的衍生于甘油、氧化丙烯和氧化乙烯的碱性聚醚醇与102g N,N-二甲氨基丙胺混合并使该混合物与290g氧化丙烯反应而不进行另外的催化。
以常规方式后处理形成的聚醚醇并将其用于生产软质聚氨酯泡沫。结果显示在聚氨酯反应中具有优异的催化作用。
实施例5
使605g来自实施例4的碱性多元醇与245g氧化丙烯反应。以常规方式后处理形成的聚醚醇并将其用于生产软质聚氨酯泡沫。结果显示在聚氨酯反应中具有优异的催化作用。
实施例6
将1080g来自实施例4的碱性多元醇与491g N,N-二(3-二甲氨基丙基)-N-异丙醇胺混合并与264g氧化乙烯反应而不进行另外的催化。
以常规方式后处理形成的聚醚醇并将其用于生产软质聚氨酯泡沫。结果显示在聚氨酯反应中具有优异的催化作用。
实施例7
将1080g来自实施例4的碱性多元醇与375g二(N,N-二甲基-3-氨基丙基)胺混合并在不进行另外的催化下首先与349g氧化丙烯反应,然后在不进行进一步的后处理下与88g氧化乙烯反应。
以常规方式后处理形成的聚醚醇并将其用于生产软质聚氨酯泡沫。结果显示在聚氨酯反应中具有优异的催化作用。
实施例8(对比例)
为了生产半硬质聚氨酯泡沫,将由46重量份2090(Elastogran GmbH)、45重量份2095(Elastogran GmbH)、2重量份1,4-丁二醇、0.5重量份三乙醇胺、3重量份线性聚酯(基于己二酸、乙二醇、丁二醇和M10R,OH数:34)、0.3份二甲氨基丙胺引发的聚丙二醇(OH数:250)、0.5份乳化剂(基于用2046和聚氧化乙烯衍生物改性的马来酸酐和α-烯烃的嵌段聚合物)、0.05份B8680(Goldschmidt)、2份水和1份来自实施例2的自催化多元醇组成的多元醇组分与由衍生于MI、ME、M 20 W和2047(Elastrogan GmbH)的预聚物(NCO含量:28%)组成的异氰酸酯组分在指数为0.96下混合并将发泡混合物倾入尺寸为20cm×20cm×4cm且加热到44℃的铝模具中,得到密度为100kg/m3的垫。
按照测试方法VDA 278对该泡沫进行测试的结果显示以VOC值释放出20ppm含有二甲氨基的分子。
实施例9(根据本发明)
以类似于实施例8的方式生产泡沫,不同的是使用3.94份来自实施例3的自催化多元醇代替1份来自实施例2的自催化多元醇。
按照测试方法VDA 278对该泡沫进行测试的结果显示以VOC值释放出0ppm含有二甲氨基的分子。当使用根据本发明制备的自催化多元醇时,该泡沫的胺释放因此得到显著降低。
Claims (9)
1.一种通过使H官能起始剂物质与烯化氧反应而制备自催化聚醚醇的方法,其中H官能起始剂物质含有至少一个在氨基甲酸酯反应中呈催化活性的氨基和至少一个对烯化氧呈反应性的基团,该方法包括:
a)将起始剂物质溶于溶剂中,
b)使该溶液与烯化氧反应,
其中溶剂是羟基数为20-1200mg KOH/g且官能度为2-8的聚醚醇或对烯化氧呈化学惰性的有机溶剂。
2.如权利要求1所要求的方法,其中溶剂是羟基数为20-100mgKOH/g且官能度为2-3的聚醚醇。
3.如权利要求1所要求的方法,其中将通过在碱催化剂存在下将烯化氧加成到H官能起始剂物质上而制备并且在烯化氧的加成反应之后不从中除去催化剂的聚醚醇用作溶剂。
4.如权利要求1所要求的方法,其中将通过在碱催化剂存在下将烯化氧加成到H官能起始剂物质上而制备并且在烯化氧的加成反应之后不从中除去催化剂的聚醚醇用作溶剂。
5.如权利要求2所要求的方法,其中将通过在碱催化剂存在下将烯化氧加成到H官能起始剂物质上而制备并且在烯化氧的加成反应之后不从中除去催化剂的聚醚醇用作溶剂。
6.如权利要求1所要求的方法,其中步骤b)在碱催化剂存在下进行。
7.如权利要求1所要求的方法,其中基于所有H官能起始剂物质的重量,步骤b)中的催化剂用量为0.1-3.0重量%。
8.如权利要求1-5中任何一项所要求的方法,其中主要将氧化乙烯、氧化丙烯和/或氧化丁烯用作烯化氧。
9.如权利要求1-5中任何一项所要求的方法,其中含有至少一个在氨基甲酸酯反应中呈催化活性的氨基和至少一个对烯化氧呈反应性的基团的起始剂物质选自二甲氨基乙胺、二甲氨基丙胺、二乙氨基乙胺、二乙氨基丙胺、N-(3-二甲氨基丙基)-N,N-二异丙醇胺、二甲基乙醇胺、N,N-二甲氨基乙基·N’-甲基-N’-羟乙基氨基乙基醚、N,N-二(3-二甲氨基丙基)氨基-2-丙醇胺、二(N,N-二甲基-3-氨基丙基)胺、N,N-二甲氨基乙氧基乙醇、N-(3-氨基丙基)咪唑、N-(2-二甲氨基乙基)-N-甲基乙醇胺、N-(2-羟丙基)咪唑、二甲氨基己醇以及至少两种所述化合物的混合物。
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CN1130196A (zh) * | 1994-10-22 | 1996-09-04 | Basf公司 | 低结雾的聚氨酯泡沫的制备方法和用于此目的的特定的聚亚氧烷基一多元醇 |
US20020120026A1 (en) * | 2000-12-20 | 2002-08-29 | Schilling Steven L. | Co-initiated polyols useful for the production of rigid polyurethane foams |
WO2003029320A1 (en) * | 2001-10-01 | 2003-04-10 | Dow Global Technologies Inc. | Autocatalytic polyols with gelling characteristics and polyurethane products made therefrom |
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US20060258832A1 (en) | 2006-11-16 |
CN1835982A (zh) | 2006-09-20 |
WO2005014685A1 (de) | 2005-02-17 |
ATE545670T1 (de) | 2012-03-15 |
US7759521B2 (en) | 2010-07-20 |
EP1656406B1 (de) | 2012-02-15 |
DE10337319A1 (de) | 2005-03-17 |
ES2377256T3 (es) | 2012-03-26 |
EP1656406A1 (de) | 2006-05-17 |
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