CA2143972A1 - High functionality polyether polyols containing hydroxyl groups and a process for the production thereof - Google Patents
High functionality polyether polyols containing hydroxyl groups and a process for the production thereofInfo
- Publication number
- CA2143972A1 CA2143972A1 CA002143972A CA2143972A CA2143972A1 CA 2143972 A1 CA2143972 A1 CA 2143972A1 CA 002143972 A CA002143972 A CA 002143972A CA 2143972 A CA2143972 A CA 2143972A CA 2143972 A1 CA2143972 A1 CA 2143972A1
- Authority
- CA
- Canada
- Prior art keywords
- functionality
- compound
- polyether polyol
- polyether
- mol
- 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.)
- Abandoned
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 87
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 73
- 150000003077 polyols Chemical class 0.000 title claims abstract description 59
- 229920005862 polyol Polymers 0.000 title claims abstract description 56
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 27
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000007513 acids Chemical class 0.000 claims abstract description 6
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 239000007858 starting material Substances 0.000 description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- -1 propenyl alcohols Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- DWOBGCPUQNFAFB-UHFFFAOYSA-N 2-benzylaniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1 DWOBGCPUQNFAFB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- AMUBKBXGFDIMDJ-UHFFFAOYSA-N 3-heptyl-1,2-bis(9-isocyanatononyl)-4-pentylcyclohexane Chemical compound CCCCCCCC1C(CCCCC)CCC(CCCCCCCCCN=C=O)C1CCCCCCCCCN=C=O AMUBKBXGFDIMDJ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WDTRNCFZFQIWLM-UHFFFAOYSA-N 4-benzylaniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1 WDTRNCFZFQIWLM-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- UNLSXXHOHZUADN-UHFFFAOYSA-N barium cyanide Chemical compound [Ba+2].N#[C-].N#[C-] UNLSXXHOHZUADN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 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 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Relatively high functionality, modified polyether polyols containing hydroxyl groups and having a very low double bond content with a total functionality of (nx-my) are produced by reacting n mol of a starting polyether polyol having a functionality x, optionally in the presence of a catalyst, with m mol of a compound containing at least one group reactive with hydroxyl functions, which compound has a functionality y at a temperature of from about 40 to about 200°C. The compound containing at least one group which is reactive with hydroxyl groups is selected from (a) diisocyanates and polyisocyanates and (b) polycarboxylic acids and their anhydrides.
Description
` - 21~3972 Bg/m-637PE
~IIGE~ FUNCTIONALITY POLY~; l H~;K
POLYOLS CONTAIN~NG ~YDROXYL GROUPS
AND A PROCESS FOR TE~E PRODUCTION TEIEREOF
BACKGROUND OF T~E ~VENTION
This invention relates to high functionality, modif~led polyether polyols containing hydroyl groups and having a very low content of double bonds and to a process for the production thereof.
Polyether polyols may be obtained by polyaddition of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide onto 5 compounds with active hydrogen atoms (starter compounds) such as alcohols, amines, acid amides, and phenols. Such polyether polyols are useful for the production of polyurethane plastics, surfactants and lubricants.
Polyaddition of epoxides onto starter compounds is generally carried out using an alkali catalyst. The most commonly used alkali catalysts are alkali hydroxides. However, polyether polyols produced with alkali catalysts are contaminated with monofunctional polyethers having 25 tèrminal double bonds. These monofunctional polyethers are formed by rearrangement of epoxides (e.g., propylene oxide) to form allyl or propenyl alcohols which may then act as starters for further alkali- --catalyzed polyaddition. In an analogous reaction, ethylene oxide produces monofunctional ethers with a terminal vinyl ether structure.
The proportion of monofunctional polyethers increases only as the - resultant polyethers increase in chain length or decrease in OH value.
For this reason, it is virtually impossible to produce polyethers in which the individual polyether chains achieve molecular weights of from about 2,000 to about 2,500 which are free of monofunctional polyethers having terminal doublë- bonds from starter compounds and propylene oxide.
Le A 30 007-FC - 1-The relatively high contenl of monofunctional polyethers obtained in conventional alkali hydroxide catalyzed processes rednces the desired functionality of the polyether. Such a loss of functionality is not desirable in the production of for example polyu, etl ,a"e elaslor"ers.
s In general monofunctional materials are disadvantageous in polyurethane polyaddilion processes because they act as chai terminators.
It is known from the literature that polyether polyols produced using metal-cyanide coil,plexes as the catalyst (U.S. Patent 4 985 491) l0 have very low conlents of monofunctional polyethers with terminal double bonds. This process also allows the production of higher molecular weight polyether polyols than does the alkali-catalyzed process. One disadvantage of this known process is the use of a metal-cyanide catalyst. Ethylene oxide addition cannot be salisra.;torily performed (EP-5 A 0 406 440 page 3 lines 24-27) using a metal-cyanide catalyst.
Further removal of the metal cyanide catalyst and disposal by any of the known processes is complicated.
EP-A 0 369 487 recol"r"el,ds the use of catalyst containing barium and strontium for the production of polyether polyols having low 20 double bond cGnlel,ls. Use of these catalysts is very complicated and consequently uneconomical. Removal of these catalysts may also be problematic.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for 25 the production of polyether polyols with a functionality at least as high as that of starter without the use of alkali hydroxide metal cyanide barium or strontium catalysts.
It is another object of the ~ ese"l invention to provide a process for the production of high functionality polyether polyols than that 30 of starters having low double bond conlenLs in which the use of uneconomical catalysts is unnecessary.
It is a further object of the present invention to provide high functionality polyether polyols having low double bond conte"ls than those generated by alkali catalysed process.
These and other objects which will be appare"l to those skilled 5 in the art are accomplished by reacting n mols of a starting polyether polyol having a functionality of x with m mols of a compound having a functionality of y which compound has groups that are reactive with hydroxyl groups. If more than one starting polyether polyol is used, the value of x for each polyether polyol may be the same or it may be 10 different. The polyether polyol(s) produced by this reaction is(are) highly functional, modified polyether polyol(s) having a total functionality of (nx-my).
DETAILED DESCRIPTION OF THE INVENTION
In the practice of the present invention, n mols of at least one 15 hydroxy-functional starting polyether having a functionality x (where more than one hydroxy-functional sla, li"g polyether is used, x may represent the same or a dirrerenl value for each polyether polyol) are reacted with m mol of a compound having a functionality y and groups which are reactive with hydroxyl groups to produce one or more highly functional 20 modified polyethers conlaining hydroxyl groups and having a total functionality of (nx-my).
For example, a modified polyether polyol having a calculated functionality of 4 may be obtained by reacting two mols of a trifunctional polyether polyol with one mol of a difunctional compound having groups 2 5 reactive with hydroxyl functions. Two mols of a hexafunctional polyol produce a modified polyether polyol having a calculated functionality of 10 when that hexafunctional polyol is reacted with 1 mol of a hydroxyl-reactive compound having a functionality of 2.
Polyethers with functionalities such as 10 are not obtainable by 3 o conventional polyether production processes.
The presenl invention provides relatively highly functional, modified polyether polyols containing hydroxyl groups and having a very low double bond contenl with a total functionality of (nx-my) which could be two or higher. These modified polyether polyols are produced by reacting n mol of a starting polyether polyol of a functionality x, optionally in the presence of a catalyst, with m mol of a cGr"pound containing at 5 least one group reactive with hydroxyl functions, which compound has a functionality y and is selected from (a) polyisocyanates and (b) poly-carboxylic acids at 40 to 200C.
It is prererr~d that the compound cG"laining at least one group reactive with hydroxyl functions be selected from (a) di- or triisocyanates 0 and (b) di- or tricarboxylic acids. It is also prerer,ed that the starting polyether polyol(s) have a functionality of from about 2 to about 8 and an OH value of from about 28 to about 400.
In prerer,ed embodiments of the process of the present invention, the reaction of the starting polyether polyol with the compound 5 containing groups reactive with hydroxyl functions is pe, rormed either (a) at 40 to 1 50C, most prererably at 60 to 1 20C when a polyisocyanate is used as the hydroxyl-reactive compound or (b) at 120 to 220C, most prereral)ly at 130 to 1 80C when a polycarboxylic acid is used as the hydroxyl-reactive compound.
Reaction of the starting polyether polyol(s) with a polyisocyanate may be performed either discontinuously in a reaction vessel or continuously in a tubular rea~or. The starting polyether polyol and the polyisocyanate may be fed separately into the tubular reactor, upstream from which a static mixer is arranged.
2 5 Relatively highly functional, modified polyether polyols conlaining hydroxyl groups and having a very low double bond content and a total functionality of (nx-my) obtainable by reacting n mol of starting polyether polyols of variable functionality x and chain length with m mol of a polyisocyanate or polyca, I oxylic acid in accordance with the process of the present invention are particularly prerer,ed.
Starting polyethers useful in the process of the present invention include the alkoxylation products of starter compounds having molecular weights of up to 400 and having from 2 to 8 hydroxyl, thiol ~14~972 and/or amino groups. Specific examples of starter co, ~ ounds from which suitable starter polyether polyols may be made include: ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, tl imetllylGlpropa"e, glycerol, 5 pentaerythritol, sorbitol, sugar (sucrose), degraded starch, water, methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, o- and p-toluidine, a"~-naphlllylamine, ammonia, ethylenediamine, propylenediamine, 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, o-, m- and p-phenylenediamine, 2,4-, 2,6-0 tolylenediamine, 2,2'-, 2,4- and 4,4'-diaminodiphenylmethane and diethylenediamine, or mixtures of these compounds. Ethylene oxide, propylene oxide, butylene oxide and mixtures thereof may be used as the epoxides.
Synthesis of the polyether chains by alkoxylation may be 5 carried out with only a monomeric epoxide or it may also proceed rando",ly or in blocks with two or more dirrere"t monomeric epoxides.
Further details with respect to the production of such starter polyethers may be found in Ullmanns, EncycloPadie der industriellen Chemie.
English edition, 1992, Volume A21, pages 670-671. The sta, ling 2 o polyethers used in the process of the present invention preferably have a functionality of from about 2 to about 8 and an OH value of from about 28 to about 400.
Diisocyanates and polyisocyanates which are useful as the cor"pound having groups which are reactive with hydroxyl groups 25 include: aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates. Such isocyanates are described, for example, by 21~97~ -W. Siefken in Justus I iebigs Annalen der Chemie, 562, pages 75 to 136.
Examples of suitable isocyanates are those represented by the formula Q(NCO)n in which 5 n represents 2 or3, and Q represents an aliphatic hydrocarbon residue having from 2 to 18 (preferably 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon residue having from 4 to 15 (preferably 5 to 10) carbon atoms, an aromatic hydrocarbon residue having from 6 to 15 (preferably 6 to 13) carbon atoms or an araliphatic hydrocarbon residue ha~ing from 8 to 15 (preferably:8 to 13) carbon atoms.
Specific examples of suitable-isocyanates include: hexamethylene diisocyanate (HDI); -1,4-cyclohexyl diisocyanate and the isomers thereof;
isophorone diisocyanate (IPDI); dimeryl diisocyanate (Ullmanns 15 Encyclopadie der Industriellen Chemie, English edition, 1992, Volume A21, bottom of page 668); 4,4'-diisocyanato-dicyclohexylmethane and the isomers thereof; 2,4-tolylene diisocyanate and the isomers thereof (TDI);
~IIGE~ FUNCTIONALITY POLY~; l H~;K
POLYOLS CONTAIN~NG ~YDROXYL GROUPS
AND A PROCESS FOR TE~E PRODUCTION TEIEREOF
BACKGROUND OF T~E ~VENTION
This invention relates to high functionality, modif~led polyether polyols containing hydroyl groups and having a very low content of double bonds and to a process for the production thereof.
Polyether polyols may be obtained by polyaddition of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide onto 5 compounds with active hydrogen atoms (starter compounds) such as alcohols, amines, acid amides, and phenols. Such polyether polyols are useful for the production of polyurethane plastics, surfactants and lubricants.
Polyaddition of epoxides onto starter compounds is generally carried out using an alkali catalyst. The most commonly used alkali catalysts are alkali hydroxides. However, polyether polyols produced with alkali catalysts are contaminated with monofunctional polyethers having 25 tèrminal double bonds. These monofunctional polyethers are formed by rearrangement of epoxides (e.g., propylene oxide) to form allyl or propenyl alcohols which may then act as starters for further alkali- --catalyzed polyaddition. In an analogous reaction, ethylene oxide produces monofunctional ethers with a terminal vinyl ether structure.
The proportion of monofunctional polyethers increases only as the - resultant polyethers increase in chain length or decrease in OH value.
For this reason, it is virtually impossible to produce polyethers in which the individual polyether chains achieve molecular weights of from about 2,000 to about 2,500 which are free of monofunctional polyethers having terminal doublë- bonds from starter compounds and propylene oxide.
Le A 30 007-FC - 1-The relatively high contenl of monofunctional polyethers obtained in conventional alkali hydroxide catalyzed processes rednces the desired functionality of the polyether. Such a loss of functionality is not desirable in the production of for example polyu, etl ,a"e elaslor"ers.
s In general monofunctional materials are disadvantageous in polyurethane polyaddilion processes because they act as chai terminators.
It is known from the literature that polyether polyols produced using metal-cyanide coil,plexes as the catalyst (U.S. Patent 4 985 491) l0 have very low conlents of monofunctional polyethers with terminal double bonds. This process also allows the production of higher molecular weight polyether polyols than does the alkali-catalyzed process. One disadvantage of this known process is the use of a metal-cyanide catalyst. Ethylene oxide addition cannot be salisra.;torily performed (EP-5 A 0 406 440 page 3 lines 24-27) using a metal-cyanide catalyst.
Further removal of the metal cyanide catalyst and disposal by any of the known processes is complicated.
EP-A 0 369 487 recol"r"el,ds the use of catalyst containing barium and strontium for the production of polyether polyols having low 20 double bond cGnlel,ls. Use of these catalysts is very complicated and consequently uneconomical. Removal of these catalysts may also be problematic.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for 25 the production of polyether polyols with a functionality at least as high as that of starter without the use of alkali hydroxide metal cyanide barium or strontium catalysts.
It is another object of the ~ ese"l invention to provide a process for the production of high functionality polyether polyols than that 30 of starters having low double bond conlenLs in which the use of uneconomical catalysts is unnecessary.
It is a further object of the present invention to provide high functionality polyether polyols having low double bond conte"ls than those generated by alkali catalysed process.
These and other objects which will be appare"l to those skilled 5 in the art are accomplished by reacting n mols of a starting polyether polyol having a functionality of x with m mols of a compound having a functionality of y which compound has groups that are reactive with hydroxyl groups. If more than one starting polyether polyol is used, the value of x for each polyether polyol may be the same or it may be 10 different. The polyether polyol(s) produced by this reaction is(are) highly functional, modified polyether polyol(s) having a total functionality of (nx-my).
DETAILED DESCRIPTION OF THE INVENTION
In the practice of the present invention, n mols of at least one 15 hydroxy-functional starting polyether having a functionality x (where more than one hydroxy-functional sla, li"g polyether is used, x may represent the same or a dirrerenl value for each polyether polyol) are reacted with m mol of a compound having a functionality y and groups which are reactive with hydroxyl groups to produce one or more highly functional 20 modified polyethers conlaining hydroxyl groups and having a total functionality of (nx-my).
For example, a modified polyether polyol having a calculated functionality of 4 may be obtained by reacting two mols of a trifunctional polyether polyol with one mol of a difunctional compound having groups 2 5 reactive with hydroxyl functions. Two mols of a hexafunctional polyol produce a modified polyether polyol having a calculated functionality of 10 when that hexafunctional polyol is reacted with 1 mol of a hydroxyl-reactive compound having a functionality of 2.
Polyethers with functionalities such as 10 are not obtainable by 3 o conventional polyether production processes.
The presenl invention provides relatively highly functional, modified polyether polyols containing hydroxyl groups and having a very low double bond contenl with a total functionality of (nx-my) which could be two or higher. These modified polyether polyols are produced by reacting n mol of a starting polyether polyol of a functionality x, optionally in the presence of a catalyst, with m mol of a cGr"pound containing at 5 least one group reactive with hydroxyl functions, which compound has a functionality y and is selected from (a) polyisocyanates and (b) poly-carboxylic acids at 40 to 200C.
It is prererr~d that the compound cG"laining at least one group reactive with hydroxyl functions be selected from (a) di- or triisocyanates 0 and (b) di- or tricarboxylic acids. It is also prerer,ed that the starting polyether polyol(s) have a functionality of from about 2 to about 8 and an OH value of from about 28 to about 400.
In prerer,ed embodiments of the process of the present invention, the reaction of the starting polyether polyol with the compound 5 containing groups reactive with hydroxyl functions is pe, rormed either (a) at 40 to 1 50C, most prererably at 60 to 1 20C when a polyisocyanate is used as the hydroxyl-reactive compound or (b) at 120 to 220C, most prereral)ly at 130 to 1 80C when a polycarboxylic acid is used as the hydroxyl-reactive compound.
Reaction of the starting polyether polyol(s) with a polyisocyanate may be performed either discontinuously in a reaction vessel or continuously in a tubular rea~or. The starting polyether polyol and the polyisocyanate may be fed separately into the tubular reactor, upstream from which a static mixer is arranged.
2 5 Relatively highly functional, modified polyether polyols conlaining hydroxyl groups and having a very low double bond content and a total functionality of (nx-my) obtainable by reacting n mol of starting polyether polyols of variable functionality x and chain length with m mol of a polyisocyanate or polyca, I oxylic acid in accordance with the process of the present invention are particularly prerer,ed.
Starting polyethers useful in the process of the present invention include the alkoxylation products of starter compounds having molecular weights of up to 400 and having from 2 to 8 hydroxyl, thiol ~14~972 and/or amino groups. Specific examples of starter co, ~ ounds from which suitable starter polyether polyols may be made include: ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, tl imetllylGlpropa"e, glycerol, 5 pentaerythritol, sorbitol, sugar (sucrose), degraded starch, water, methylamine, ethylamine, propylamine, butylamine, aniline, benzylamine, o- and p-toluidine, a"~-naphlllylamine, ammonia, ethylenediamine, propylenediamine, 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, o-, m- and p-phenylenediamine, 2,4-, 2,6-0 tolylenediamine, 2,2'-, 2,4- and 4,4'-diaminodiphenylmethane and diethylenediamine, or mixtures of these compounds. Ethylene oxide, propylene oxide, butylene oxide and mixtures thereof may be used as the epoxides.
Synthesis of the polyether chains by alkoxylation may be 5 carried out with only a monomeric epoxide or it may also proceed rando",ly or in blocks with two or more dirrere"t monomeric epoxides.
Further details with respect to the production of such starter polyethers may be found in Ullmanns, EncycloPadie der industriellen Chemie.
English edition, 1992, Volume A21, pages 670-671. The sta, ling 2 o polyethers used in the process of the present invention preferably have a functionality of from about 2 to about 8 and an OH value of from about 28 to about 400.
Diisocyanates and polyisocyanates which are useful as the cor"pound having groups which are reactive with hydroxyl groups 25 include: aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates. Such isocyanates are described, for example, by 21~97~ -W. Siefken in Justus I iebigs Annalen der Chemie, 562, pages 75 to 136.
Examples of suitable isocyanates are those represented by the formula Q(NCO)n in which 5 n represents 2 or3, and Q represents an aliphatic hydrocarbon residue having from 2 to 18 (preferably 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon residue having from 4 to 15 (preferably 5 to 10) carbon atoms, an aromatic hydrocarbon residue having from 6 to 15 (preferably 6 to 13) carbon atoms or an araliphatic hydrocarbon residue ha~ing from 8 to 15 (preferably:8 to 13) carbon atoms.
Specific examples of suitable-isocyanates include: hexamethylene diisocyanate (HDI); -1,4-cyclohexyl diisocyanate and the isomers thereof;
isophorone diisocyanate (IPDI); dimeryl diisocyanate (Ullmanns 15 Encyclopadie der Industriellen Chemie, English edition, 1992, Volume A21, bottom of page 668); 4,4'-diisocyanato-dicyclohexylmethane and the isomers thereof; 2,4-tolylene diisocyanate and the isomers thereof (TDI);
4,4'-methylene-diphenyl diisocyanate and the isomers thereof (MDI); 1,5-naphthalene diisocyanate; tris-(4-isocyanatotriphenyl)-methane; and 20 mixtures of these isocyanates.
Other useful polyisocyanates include: modification products of the above-listed polyisocyanates having urethane, carbodiimide, urea or uretidione structures or mixtures thereof.
Organic polycarboxylic acids having from 2 to 20 carbon atoms, 25 preferably from 2 to 15 carbon atoms, and a functionality of 2 or 3 may be used as the polycarboxylic acid to be reacted with the starter polyether polyol in accordance with the process of the present invention.
Specific examples of suitable polycarboxylic acids include: malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic Le A 30 :~07-FC - 6 -.. . . . . . . . . . . .. . .. . . . . . . .
acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, dimeric fatty acids and trimesic acid. Either a single polycarboxylic acid or a mixture of polycarboxylic acids may be used. The polycarboxylic acids may also be 5 used in the form of their anhydrides. Phthalic anhydride and maleic anhydride are examples of suitable acid anhydrides.
If a polyisocyanate is reacted with the starter polyether polyol, .suitable optional .catalysts include.the tertiary amines and/or tin compounds known to be useful for.polyurethane reactions. If a 10 polycarboxylic acid is reacted with the.starter polyether polyol, suitable optional catalysts include the known esterification catalysts.
-In order to produce the relatively highly.functional, modified polyether polyols containing hydroxyl groups of the present invention, the polyether polyol(s) is (are) reacted with a compound containing groups 15 that are reactive with hydroxyl groups, optionally in the presence of a catalyst, at 40 to 200C.
It is preferred that this reaction be carried out at from about 40 to about 1 50C, most preferably from about 60 to about 1 20C if a polyisocyanate is being reacted with the starter polyether polyol. The 20 reaction of the present invention is preferably carried out at from about 120 to about 220C, most preferably from about 130 to about 180C if the starter polyether polyol is being reacted with a polycarboxylic acid.
The modified polyether polyols produced in accordance with the present invention are colorless to slightly colored, mobile to highly 25 viscous liquids. These modified polyether polyols have OH values of from about 10 to about 80 and a calculated molecular weight of from about 2,000 to about 32,000. The double bond content of the polyether polyols is determined using ASTM Designation: D 4671-87.
Le- A 30 :007-FC - 7 -.. . .. . . , , . . .. . . . . . . .. , . , , . . , . . . , . , ... . . , . . . ~ .
The relatively highly functional, modified polyether polyols containing hydroxyl groups of the present invention are useful in the production of optionally cellular or solid polyurethanes, such as elastomers, foams, coatings and fiber-reinforced polyurethane plastics.
5 They may also be used as intermediates for lubricants or surfactants.
Having thus described our invention, the following Examples are given as being illustrative thereof. All parts and percentages given in these Examples are parts by weight or percentages by weight, unless otherwise indicated.
- Le A -30 0-07-FC 8 -~, , _ . . . . ... .. . . ... . . . . . .. . . ~ . . . . . . . . . . .. ..
EXAMPLFS
The following starting polyethers were used in the Examples which follow:
Polyether Starter Characterization of OH value ether chains (per OH
group of the Starter) PolyetherA Propylene glycol 42 mol propylene oxide 28 -- and 14.7 mol ethylene oxide Polyether B Ethylenediamine 15.9 mol propylene 60 oxide Polyether C Sorbitol 27.5 mol propylene 28 oxide and 7.8 mol ethylene oxide Polyether D Trimethylol- 14.5 mol propylene 55 propane oxide and 3.0 mol ethylene oxide Polyether E Trimethyl ol - 0 ;322 mol propylene 880 prop2n~ oxi de ~-The polyisocyanates used in the following examples were:
Polyisocyanate 1: 4,4'-methylenediphenyl diisocyanate Polyisocyanate 2: 4,4'-methylenediphenyl diisocyanate with approximately 50 wt.% of the 2,4'- isomer 15 Polyisocyanate 3: Hexamethylene diisocyanate Polyisocyanate 4: Isophorone diisocyanate Polyisocyanate 5: 4,4'-methylenedicyclohexyl diisocyanate The polycarboxylic acid used in the following Examples was adipic acid.
Le A 30 007 9 The catalysts used in the following Examples were:
Dibutyltin dilaurate (DBTL) and Methylsulfonic acid.
Example 1:
400.0 g of Polyether A and 0.4 9 of DBTL were introduced at 60C
under a nitrogen atmosphere into a 1 liter, four-necked flask fitted with a stirrer, thermorrieter, dropping funnel, and condenser.
8.4 9 of-Polyisocyanate 3,were then added at 60C within one - - hour while the mixture was stirred. ,~he reaction mixture was then held at 120C for 20 minutes and subsequently cooled to room temperature in a water bath.
The product had the following properties:
NCO content = 0.01%
OH value = 14 mg KOH/g Viscosity, 25C = 8081 mPa~s Double bond content = 63.0 mmoUl<g Functionality (calculated) = 2 Example 2:
The procedure of Example 1 was repeated using 400.00 9 of Polyether A, 0.04 9 of DBTL and 11.10 9 of Polyisocyanate 4. The properties of the product were as follows:
NCO content = < 0.01%
OH value = 14.3 mg KOH/g ~Iscosity, 25C = 8114 mPa-s Double bond content = 63.5 mmol/lcg Functionality (calculated) = 2 ,=
Le A 30 007-FC - 10 -, . . . . , , , ... . j .. . . . . . . .. .
Fxample 3:
Example 2 was repeated with the exception that only 0.01 9 of dibutyltin laurate was used. The properties of the product were as follows:
NCO content = < 0.01%
OH value = 14.4 mg KOH/g Viscosity, 25C = 8584 mPa-s Double bond content - = 62.0 mmoVkg Functionality (calculated) = 2 F~ample 4:
- Example 3 was repeated with the exception that 460.0 g of --Polyether B and 16.0 9 of Polyisocyanate 1 were used. -The-properties of the product were as follows:
NCO content = 0.05%
OH value = 47.6 mg KOH/g Viscosity, 25C = 4360 mPa-s Double bond content -11.0 mmollkg Functionality (calcuiated) = 6 Example 5:
Example 4 was repeated with the exception that 612.0 9 of Polyether D and 25.0 9 of Polyisocyanate 2 were used. -The properties of the product were as follows:
NCO content = 0.08%
OH value = 38.8 mg KOH/g Viscosity, 25C = 7165 mPa-s Double bond content = 26 mmol/kg Functionality (calculated) = 4 Le~ A :30 :007-FC - 11 -. .. . .. . . . ... . .. .. . .
Fxample 6:
Example 5 was repeated with the exception that 384.0 9 of Polyether C and 20.0 9 of Polyisocyanate 2 were used. The properties of the product were as follows:
NCO content = 0.01%
OH value = 48.2 mg KOH/g Viscosity, 25C = 7898 mPa-s Double bond content = 12.0 mmol/kg Functionality (calculated) = 10 Example 7:
4007.0 9 of Polyether A, 73.0 9 of adipic acid and 4.1 9 of ~ methylsulfonic acid were introduced at room temperature into a 10 liter - four-necked flask fitted with a stirrer,-thermometer, dropping funnel, condenser and receiver and stirred at 130C. Water was distilled off 15 during stirring. After 13.5 hours of reaction, a sample was taken and analyzed. The ester-modified polyether had the following properties:
OH value = 13.0 mg KOH/g Acid value = 0.87 mg KOH/g pH value = 3.3 Water content = 0.01%
Viscosity, 25C = 5314 mPa-s Color = colorless Double bond content = 76.0 mmol/kg Functionality (calculated) = 2 Example 8 Example 7 was repeated with the exception that 1714.0 g of Polyether D, 40.0 g of adipic acid and 0.23 g of methylsulfonic acid were used. The reaction was carried out at 130C for 34 hours and at 150C
for 12 hours. The resultant product had the following properties:
- Le A 30 007-FC 1~ -. . . . . , . . . . . . ~ . . , _ .. . . . ~ , .. .. ..
OH value = 36.3 mg KOH/g .-Acid value = 0.8 mg KOH/g pH value = 4 4 Water content . = o.o1%
Double bond content = 33 mmoUkg Viscosity at 25C = 2452 mPa-s Functionality (calculated) = 4 Fxample 9:
~. Example 6 was repeated :with the exception that 400 9 of PolyetherA, 19.8 9 of Polyether E,0.11 g-of.DBTL and 26.2 9 of Polyisocyanate 5 were used. :. The properties-of the.product were as : -follows:
NCO content = ~ 0.01%
Viscosity = 9200 mPa~s OH value = 40.1 mg KOH/g Double bond content = 58 mmoUkg Functionality (calculated) . = 3 Although the invention has been described in detail in the .-. foregoing for the purpose.of illustration, it is to be understood that such 20 - . detail is solely for that purpose and that~variations can- be made therein.
. by those skilled in the art without:departing from the.spirit and scope of . the invention except as it may be limited by the claims.
Le A ;30 007-FC - 13 -.. . .. . . . . ..
Other useful polyisocyanates include: modification products of the above-listed polyisocyanates having urethane, carbodiimide, urea or uretidione structures or mixtures thereof.
Organic polycarboxylic acids having from 2 to 20 carbon atoms, 25 preferably from 2 to 15 carbon atoms, and a functionality of 2 or 3 may be used as the polycarboxylic acid to be reacted with the starter polyether polyol in accordance with the process of the present invention.
Specific examples of suitable polycarboxylic acids include: malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic Le A 30 :~07-FC - 6 -.. . . . . . . . . . . .. . .. . . . . . . .
acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, dimeric fatty acids and trimesic acid. Either a single polycarboxylic acid or a mixture of polycarboxylic acids may be used. The polycarboxylic acids may also be 5 used in the form of their anhydrides. Phthalic anhydride and maleic anhydride are examples of suitable acid anhydrides.
If a polyisocyanate is reacted with the starter polyether polyol, .suitable optional .catalysts include.the tertiary amines and/or tin compounds known to be useful for.polyurethane reactions. If a 10 polycarboxylic acid is reacted with the.starter polyether polyol, suitable optional catalysts include the known esterification catalysts.
-In order to produce the relatively highly.functional, modified polyether polyols containing hydroxyl groups of the present invention, the polyether polyol(s) is (are) reacted with a compound containing groups 15 that are reactive with hydroxyl groups, optionally in the presence of a catalyst, at 40 to 200C.
It is preferred that this reaction be carried out at from about 40 to about 1 50C, most preferably from about 60 to about 1 20C if a polyisocyanate is being reacted with the starter polyether polyol. The 20 reaction of the present invention is preferably carried out at from about 120 to about 220C, most preferably from about 130 to about 180C if the starter polyether polyol is being reacted with a polycarboxylic acid.
The modified polyether polyols produced in accordance with the present invention are colorless to slightly colored, mobile to highly 25 viscous liquids. These modified polyether polyols have OH values of from about 10 to about 80 and a calculated molecular weight of from about 2,000 to about 32,000. The double bond content of the polyether polyols is determined using ASTM Designation: D 4671-87.
Le- A 30 :007-FC - 7 -.. . .. . . , , . . .. . . . . . . .. , . , , . . , . . . , . , ... . . , . . . ~ .
The relatively highly functional, modified polyether polyols containing hydroxyl groups of the present invention are useful in the production of optionally cellular or solid polyurethanes, such as elastomers, foams, coatings and fiber-reinforced polyurethane plastics.
5 They may also be used as intermediates for lubricants or surfactants.
Having thus described our invention, the following Examples are given as being illustrative thereof. All parts and percentages given in these Examples are parts by weight or percentages by weight, unless otherwise indicated.
- Le A -30 0-07-FC 8 -~, , _ . . . . ... .. . . ... . . . . . .. . . ~ . . . . . . . . . . .. ..
EXAMPLFS
The following starting polyethers were used in the Examples which follow:
Polyether Starter Characterization of OH value ether chains (per OH
group of the Starter) PolyetherA Propylene glycol 42 mol propylene oxide 28 -- and 14.7 mol ethylene oxide Polyether B Ethylenediamine 15.9 mol propylene 60 oxide Polyether C Sorbitol 27.5 mol propylene 28 oxide and 7.8 mol ethylene oxide Polyether D Trimethylol- 14.5 mol propylene 55 propane oxide and 3.0 mol ethylene oxide Polyether E Trimethyl ol - 0 ;322 mol propylene 880 prop2n~ oxi de ~-The polyisocyanates used in the following examples were:
Polyisocyanate 1: 4,4'-methylenediphenyl diisocyanate Polyisocyanate 2: 4,4'-methylenediphenyl diisocyanate with approximately 50 wt.% of the 2,4'- isomer 15 Polyisocyanate 3: Hexamethylene diisocyanate Polyisocyanate 4: Isophorone diisocyanate Polyisocyanate 5: 4,4'-methylenedicyclohexyl diisocyanate The polycarboxylic acid used in the following Examples was adipic acid.
Le A 30 007 9 The catalysts used in the following Examples were:
Dibutyltin dilaurate (DBTL) and Methylsulfonic acid.
Example 1:
400.0 g of Polyether A and 0.4 9 of DBTL were introduced at 60C
under a nitrogen atmosphere into a 1 liter, four-necked flask fitted with a stirrer, thermorrieter, dropping funnel, and condenser.
8.4 9 of-Polyisocyanate 3,were then added at 60C within one - - hour while the mixture was stirred. ,~he reaction mixture was then held at 120C for 20 minutes and subsequently cooled to room temperature in a water bath.
The product had the following properties:
NCO content = 0.01%
OH value = 14 mg KOH/g Viscosity, 25C = 8081 mPa~s Double bond content = 63.0 mmoUl<g Functionality (calculated) = 2 Example 2:
The procedure of Example 1 was repeated using 400.00 9 of Polyether A, 0.04 9 of DBTL and 11.10 9 of Polyisocyanate 4. The properties of the product were as follows:
NCO content = < 0.01%
OH value = 14.3 mg KOH/g ~Iscosity, 25C = 8114 mPa-s Double bond content = 63.5 mmol/lcg Functionality (calculated) = 2 ,=
Le A 30 007-FC - 10 -, . . . . , , , ... . j .. . . . . . . .. .
Fxample 3:
Example 2 was repeated with the exception that only 0.01 9 of dibutyltin laurate was used. The properties of the product were as follows:
NCO content = < 0.01%
OH value = 14.4 mg KOH/g Viscosity, 25C = 8584 mPa-s Double bond content - = 62.0 mmoVkg Functionality (calculated) = 2 F~ample 4:
- Example 3 was repeated with the exception that 460.0 g of --Polyether B and 16.0 9 of Polyisocyanate 1 were used. -The-properties of the product were as follows:
NCO content = 0.05%
OH value = 47.6 mg KOH/g Viscosity, 25C = 4360 mPa-s Double bond content -11.0 mmollkg Functionality (calcuiated) = 6 Example 5:
Example 4 was repeated with the exception that 612.0 9 of Polyether D and 25.0 9 of Polyisocyanate 2 were used. -The properties of the product were as follows:
NCO content = 0.08%
OH value = 38.8 mg KOH/g Viscosity, 25C = 7165 mPa-s Double bond content = 26 mmol/kg Functionality (calculated) = 4 Le~ A :30 :007-FC - 11 -. .. . .. . . . ... . .. .. . .
Fxample 6:
Example 5 was repeated with the exception that 384.0 9 of Polyether C and 20.0 9 of Polyisocyanate 2 were used. The properties of the product were as follows:
NCO content = 0.01%
OH value = 48.2 mg KOH/g Viscosity, 25C = 7898 mPa-s Double bond content = 12.0 mmol/kg Functionality (calculated) = 10 Example 7:
4007.0 9 of Polyether A, 73.0 9 of adipic acid and 4.1 9 of ~ methylsulfonic acid were introduced at room temperature into a 10 liter - four-necked flask fitted with a stirrer,-thermometer, dropping funnel, condenser and receiver and stirred at 130C. Water was distilled off 15 during stirring. After 13.5 hours of reaction, a sample was taken and analyzed. The ester-modified polyether had the following properties:
OH value = 13.0 mg KOH/g Acid value = 0.87 mg KOH/g pH value = 3.3 Water content = 0.01%
Viscosity, 25C = 5314 mPa-s Color = colorless Double bond content = 76.0 mmol/kg Functionality (calculated) = 2 Example 8 Example 7 was repeated with the exception that 1714.0 g of Polyether D, 40.0 g of adipic acid and 0.23 g of methylsulfonic acid were used. The reaction was carried out at 130C for 34 hours and at 150C
for 12 hours. The resultant product had the following properties:
- Le A 30 007-FC 1~ -. . . . . , . . . . . . ~ . . , _ .. . . . ~ , .. .. ..
OH value = 36.3 mg KOH/g .-Acid value = 0.8 mg KOH/g pH value = 4 4 Water content . = o.o1%
Double bond content = 33 mmoUkg Viscosity at 25C = 2452 mPa-s Functionality (calculated) = 4 Fxample 9:
~. Example 6 was repeated :with the exception that 400 9 of PolyetherA, 19.8 9 of Polyether E,0.11 g-of.DBTL and 26.2 9 of Polyisocyanate 5 were used. :. The properties-of the.product were as : -follows:
NCO content = ~ 0.01%
Viscosity = 9200 mPa~s OH value = 40.1 mg KOH/g Double bond content = 58 mmoUkg Functionality (calculated) . = 3 Although the invention has been described in detail in the .-. foregoing for the purpose.of illustration, it is to be understood that such 20 - . detail is solely for that purpose and that~variations can- be made therein.
. by those skilled in the art without:departing from the.spirit and scope of . the invention except as it may be limited by the claims.
Le A ;30 007-FC - 13 -.. . .. . . . . ..
Claims (14)
1. A process for the production of a highly functional, modified polyether polyol containing hydroxyl groups and having a low double bond content which polyether polyol has a functionality of nx-my comprising reacting (i) n mol of a polyether polyol having a functionality of x with (ii) m mol of a compound having a functionality of y which compound is selected from polyisocyanates and polycarboxylic acids or anhydrides thereof-, at a temperature of from about 40 to about 200°C.
2. The process of Claim 1. in which a. catalyst is present during the reaction.
3. The process of Claim 1 in which compound (ii) is selected from diisocyanates, triisocyanates, dicarboxylic acids, or tricarboxylic acids.
4. The process of Claim 3 in which polyether polyol (i) has a functionality of from 2 to 8 and an OH value of from about 28 to about 200.
5. The process of. Claim 1 in which. polyether polyol (i) has a functionality of from 2 to 8 and an OH value of from about 28 to about 200.
6. The process of Claim 1 in which compound (ii) is a polyisocyanate: and the reaction temperature is from about 40 to about 150°C.
7. The process of Claim 1 in which compound (ii) is a polyisocyanate and the reaction temperature is from about 60 to about 120°C.
8. The process of Claim 1 in which compound (ii) is a polycarboxylic acid and the reaction temperature is from about 120 to about 220°C.
9. The process of Claim 1 in which compound (ii) is a polycarboxylic acid and the reaction temperature is from about 130 to about 180°C.
10. The process of Claim 1 in which the process is carried out on a discontinuous basis in a reaction vessel.
11. The process of Claim 1 in which the process is carried out on a continuous basis in a tubular reactor.
12. The process of Claim 11 in which polyether polyol (i) and compound (ii) are fed into the tubular reactor separately at a point positioned up-stream from a static mixer.
13. A modified polyether polyol produced by the process of Claim 1.
14. The modified polyether polyol of Claim 13 produced from a mixture of starting polyether polyols formed from polyether polyols having different values of x and different chain lengths.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4407904.4 | 1994-03-09 | ||
DE4407904A DE4407904A1 (en) | 1994-03-09 | 1994-03-09 | Process for the preparation of higher functional, hydroxyl-containing polyether polyols |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2143972A1 true CA2143972A1 (en) | 1995-09-10 |
Family
ID=6512302
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002143972A Abandoned CA2143972A1 (en) | 1994-03-09 | 1995-03-06 | High functionality polyether polyols containing hydroxyl groups and a process for the production thereof |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0671424B1 (en) |
JP (1) | JPH07286039A (en) |
AT (1) | ATE175218T1 (en) |
BR (1) | BR9501005A (en) |
CA (1) | CA2143972A1 (en) |
DE (2) | DE4407904A1 (en) |
DK (1) | DK0671424T3 (en) |
ES (1) | ES2125501T3 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6548564B1 (en) | 2001-12-13 | 2003-04-15 | Bayer Corporation | Polyether polyols with increased functionality |
US6599952B2 (en) | 2001-12-13 | 2003-07-29 | Bayer Corporation | Polyether polyols with increased functionality |
US6753402B1 (en) | 1999-10-12 | 2004-06-22 | Basf Aktiengesellschaft | Polyester-polyether block copolymers |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6001935A (en) * | 1997-11-10 | 1999-12-14 | Stephan Company | Durable hydrophilic polymer coatings |
EP0946811B1 (en) * | 1996-12-18 | 2002-09-18 | Stepan Company | Durable hydrophilic polymer coatings |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3919172A (en) * | 1972-10-30 | 1975-11-11 | California Inst Of Techn | Method of preparing polyesters from polymeric polyols and dianhydrides |
US4242490A (en) * | 1979-07-20 | 1980-12-30 | The General Tire & Rubber Company | Thermoset polyurethane prepared from a polypropylene ether triol obtained using a double metal cyanide complex catalyst, ethylene glycol and tolylene diisocyanate |
JPS57109825A (en) * | 1980-12-26 | 1982-07-08 | Kao Corp | Preparation of novel polyester resin |
US5319006A (en) * | 1992-11-23 | 1994-06-07 | Arco Chemical Technology, L.P. | Preparation of polyesters from polyethers by an ester-insertion process |
-
1994
- 1994-03-09 DE DE4407904A patent/DE4407904A1/en not_active Withdrawn
-
1995
- 1995-02-24 DE DE59504657T patent/DE59504657D1/en not_active Expired - Fee Related
- 1995-02-24 AT AT95102674T patent/ATE175218T1/en not_active IP Right Cessation
- 1995-02-24 EP EP95102674A patent/EP0671424B1/en not_active Expired - Lifetime
- 1995-02-24 ES ES95102674T patent/ES2125501T3/en not_active Expired - Lifetime
- 1995-02-24 DK DK95102674T patent/DK0671424T3/en active
- 1995-03-06 CA CA002143972A patent/CA2143972A1/en not_active Abandoned
- 1995-03-07 JP JP7072475A patent/JPH07286039A/en active Pending
- 1995-03-08 BR BR9501005A patent/BR9501005A/en not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6753402B1 (en) | 1999-10-12 | 2004-06-22 | Basf Aktiengesellschaft | Polyester-polyether block copolymers |
US6548564B1 (en) | 2001-12-13 | 2003-04-15 | Bayer Corporation | Polyether polyols with increased functionality |
US6599952B2 (en) | 2001-12-13 | 2003-07-29 | Bayer Corporation | Polyether polyols with increased functionality |
Also Published As
Publication number | Publication date |
---|---|
BR9501005A (en) | 1995-10-31 |
ES2125501T3 (en) | 1999-03-01 |
DE59504657D1 (en) | 1999-02-11 |
DK0671424T3 (en) | 1999-06-23 |
EP0671424A1 (en) | 1995-09-13 |
DE4407904A1 (en) | 1995-09-14 |
ATE175218T1 (en) | 1999-01-15 |
JPH07286039A (en) | 1995-10-31 |
EP0671424B1 (en) | 1998-12-30 |
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