CN116333285A - 一种低反应活性聚酯多元醇及其制备方法和应用 - Google Patents
一种低反应活性聚酯多元醇及其制备方法和应用 Download PDFInfo
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- polyester polyol
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 38
- 239000000853 adhesive Substances 0.000 claims abstract description 37
- 239000004814 polyurethane Substances 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- -1 hydroxyl polyol Chemical class 0.000 claims abstract description 13
- ZXYFGZNMDRNOGQ-UHFFFAOYSA-N ac1lawgt Chemical compound [S]O ZXYFGZNMDRNOGQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 21
- 230000009257 reactivity Effects 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 229940014800 succinic anhydride Drugs 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000001384 succinic acid Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 2
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical group [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- JSMLXTZCMDYUQJ-UHFFFAOYSA-N dithiane-3,4-diol Chemical compound OC1CCSSC1O JSMLXTZCMDYUQJ-UHFFFAOYSA-N 0.000 claims description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- YPGMOWHXEQDBBV-QWWZWVQMSA-N (4S,5S)-1,2-dithiane-4,5-diol Chemical compound O[C@@H]1CSSC[C@H]1O YPGMOWHXEQDBBV-QWWZWVQMSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 10
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 229960003180 glutathione Drugs 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YUEDZVRMWQBEPT-UHFFFAOYSA-N CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O Chemical compound CC1=CC=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C.N=C=O.N=C=O.N=C=O.N=C=O YUEDZVRMWQBEPT-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- YPGMOWHXEQDBBV-UHFFFAOYSA-N dithiane-4,5-diol Chemical compound OC1CSSCC1O YPGMOWHXEQDBBV-UHFFFAOYSA-N 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 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 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy 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
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
-
- 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
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开一种低反应活性聚酯多元醇及其制备方法,所述低反应活性聚酯多元醇由100摩尔份的二元酸/酸酐、90‑150摩尔份的伯羟基多元醇和1‑50摩尔份的非伯羟基含硫多元醇经酯化和缩聚反应制得。使用本发明聚酯多元醇制备双组分聚氨酯胶粘剂产品的固化时间和可操作时间适中,且具有易清理特性。
Description
技术领域
本发明属于聚酯多元醇领域和聚氨酯领域,具体的涉及一种低反应活性聚酯多元醇及其制备方法和应用。
背景技术
聚氨酯胶粘剂是分子链中含有氨酯基和/或异氰酸酯基的胶粘剂,其性能优越,故在工业和民用许多领域得到广泛应用。其中的双组分聚氨酯胶粘剂是聚氨酯胶粘剂中最重要的一大类,通常由主剂(羟基组分或端基NCO的聚氨酯预聚体)和固化剂(含游离异氰酸酯基团的组分或多元醇/胺)两组分组成,其在使用过程中需将两种组分混合,使两者在一定条件下固化,从而产生较高的粘结强度。
聚酯多元醇作为制备聚氨酯胶粘剂的原料之一,主要通过多元醇与多元酸或酸酐等在存在或不存在催化剂的条件下缩聚制得,其可为聚氨酯材料提供较好的粘剂强度和耐候等性能。
但是聚酯多元醇与异氰酸酯的反应速率对双组分聚氨酯胶粘剂的固化时间具有重要影响。聚酯多元醇与异氰酸酯的反应速率过慢,两者固化速率慢,胶粘剂的固化时间长,但是初粘强度弱;聚酯多元醇与异氰酸酯的反应速率过快,两者固化速率快,胶粘剂的固化时间短,导致可操作时间短。当聚酯多元醇与异氰酸酯反应速率较慢时,可通过添加催化剂加快聚合反应,相较而言,过高的反应速率则更加难以控制。
为降低聚酯多元醇与异氰酸酯的反应速率,延长双组分胶粘剂的操作时间、施工时间,研究学者们做了大量研究。B.Fortunato等通过加入含磷助剂,络合酯化催化剂,从而降低聚酯多元醇与异氰酸酯的反应活性,但是该类酸性助剂会使聚氨酯胶粘剂的耐水解性能降低;专利CN 1759132A则通过使以锡类催化剂制备的聚酯多元醇与氧气接触,从而降低反应活性,但是该法可能会使聚酯多元醇产品氧化,色号升高,同时该法增加了后处理过程,工艺繁琐。
综上,聚酯多元醇产品的反应活性对双组分聚氨酯胶粘剂的固化时间和可操作时间具有重要影响,因此,开发一种具有低反应活性的聚酯多元醇显得尤为重要。
发明内容:
本发明提供一种低反应活性聚酯多元醇及其制备方法。本发明制备的聚酯多元醇与异氰酸酯单体的反应速率适中,制备得到双组分聚氨酯胶粘剂固化速度适中,可操作时间合适,且该胶粘剂具有易清理特性。
本发明为达到上述目的,采用的技术方案如下:
一方面,本发明提供的低反应活性聚酯多元醇,由以下组分组成:
A)二元酸/酸酐:100摩尔份;
B)伯羟基多元醇:90-150摩尔份,优选为100-130摩尔份;
C)非伯羟基含硫多元醇:1-50摩尔份,优选为10-40摩尔份。
本发明中,所述组分A中二元酸选自碳原子数为2-20个的脂肪族二元羧酸或芳香族二元羧酸,所述酸酐选自碳原子数为4-20个的脂肪族酸酐或芳香族酸酐;在一些具体的实施方式中,所述二元酸选自丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二碳二元酸、呋喃二甲酸、邻苯二甲酸、间苯二甲酸或对苯二甲酸中的一种或多种,所述二元酸更优选为丁二酸和/或己二酸;所述酸酐选自丁二酸酐、戊二酸酐、己二酸酐、马来酸酐、四氢苯酐、六氢苯酐或邻苯二甲酸酐中的一种或多种,所述酸酐更优选为丁二酸酐。
本发明中,所述组分B伯羟基多元醇选自碳原子数为2-20个的多元醇,且多元醇上羟基均为伯羟基;在一些具体的实施方式中,所述组分B选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、十二碳二元醇、1,5-戊二醇、1,4-环己烷二甲醇、甘油、季戊四醇中的一种或多种;在一些更优选的实施方式中,所述组分B选自1,4-丁二醇、1,6-己二醇中的一种或多种。
本发明中,所述组分C非伯羟基含硫多元醇选自1,1-二硫代二丙-2-醇、3,3-二硫代二丁-2-醇、1,1-三硫代二丁-2-醇、4,5-二羟基-1,2-二噻烷、3,4-二羟基-1,2-二噻烷、1,2,7,8-四羟基-4,5,10,11-四硫环十二烷中的一种或多种;优选地,所述组分C为1,1-二硫代二丙-2-醇。
其中,与伯羟基多元醇相比,仲羟基和叔羟基多元醇的反应活性较低,因此在制备聚酯多元醇时,更易形成末端为仲羟基或叔羟基的聚酯多元醇。
本发明中所述聚酯多元醇的酸值为0.01-10.00mg KOH/g,羟值为10-200mg KOH/g;在一些优选的实施方式中,所述聚酯多元醇的酸值为0.03-5.00mg KOH/g,所述聚酯多元醇的羟值为30-150mg KOH/g;在一些更优选的实施方式中,所述聚酯多元醇的酸值为0.05-2.00mg KOH/g,所述聚酯多元醇的羟值为56-112mg KOH/g。
另一方面,本发明还提供了聚酯多元醇的制备方法,包含如下步骤:1)在惰性气体存在下,将所述组分A和组分B混合后,在140-160℃下反应0.5h-1.5h;2)升温至170-180℃下反应0.5h-1.0h,加入组分C,继续反应0.5-1.0h;3)升温至210-230℃,任选地加入催化剂反应后,再在真空下(比如,-0.09MPa)继续反应至体系的酸值为0.01-10.00mg KOH/g,且羟值为10-200mg KOH/g,得到所述聚酯多元醇。
在本发明提供的聚酯多元醇中,以所述组分A)、组分B)和组分C)的总质量计,所述催化剂的用量为0-500ppm,优选为40-300ppm。
在一些具体的实施方式中,所述催化剂选自钛类催化剂、锡类催化剂或锑类催化剂中的一种或多种;所述钛类催化剂选自钛酸正丁酯、钛酸四异丙酯或二氧化钛;所述锡类催化剂选自二月桂酸二丁基锡、辛酸亚锡或氯化亚锡;所述锑类催化剂选自醋酸锑、三氧化二锑或乙二醇锑;在一些优选的方式中,所述催化剂采用钛类催化剂,更优选为钛酸正丁酯或钛酸四异丙酯。
再一方面,本发明还提供了一种双组分聚氨酯胶粘剂,所述聚氨酯胶粘剂由以下组分组成:
主剂:低反应活性聚酯多元醇;
固化剂:多异氰酸酯化合物。
本发明中,所述双组分聚氨酯胶粘剂中低反应活性聚酯多元醇与多异氰酸酯化合物的质量比为1:0.1-2。
本发明中,所述多异氰酸酯化合物选自多亚甲基多苯基异氰酸酯(PAPI)、TDI三聚体、HDI三聚体、HDI缩二脲、IPDI三聚体、TDI-TMP加成物、TDI-甘油加成物、三苯基甲烷三异氰酸酯(TTI)、硫代磷酸三(4-苯基异氰酸酯)和二甲基三苯基甲烷四异氰酸酯(JQ-5)中的一种或多种;更优选为TDI三聚体或TDI-TMP加成物中的一种或多种。
本发明具有如下有益效果:
1)本发明通过使用末端为仲羟基或叔羟基的含硫多元醇,制备末端含有部分仲羟基或叔羟基的聚酯多元醇,降低其与异氰酸酯单体的反应速率;
2)本发明通过在实验后期加入仲羟基或叔羟基多元醇,可有效提高末端仲羟基或叔羟基的比例;
3)本发明提供的聚酯多元醇与异氰酸酯化合物反应速率适中,可调整双组分胶粘剂的固化时间和可操作时间;
4)使用本发明提供的聚酯多元醇制备的双组分聚氨酯胶粘剂可通过GSH溶液进行擦拭,从而使二硫键断裂,胶粘剂交联度和亲水性增强,更易于清理。
具体实施方式
为了更好的理解本发明的技术方案,下面结合实施例进一步阐述本发明的内容,但本发明的内容并不仅仅局限于以下实施例。
以下实施例和对比例使用的原料均为商业化的化学品。
本发明的实施例和对比例中产品性能测定采用如下方法:
酸值的测定:参考化工行业标准HG/T 2708-1995;
羟值的测定:参考化工行业标准HG/T 2709-1995;
聚酯多元醇反应活性测试方法参考HG/T 2707-95,并进行优化:
配方:
聚酯多元醇:100g;
实验步骤:将称量好的聚酯多元醇和MDI置于70℃烘箱中恒温2h,将MDI倒至聚酯多元醇中,并开始计时,在700r/min的转速下搅拌1min,然后利用粘度计测试体系的粘度,直至粘度达到200000cP,停止计时,记录时间为T,时间T越长,说明聚酯多元醇的反应活性越低。
聚氨酯胶黏剂的剥离和清除特性通过以下方式进行评测:
耐溶剂擦拭性测试:将表面涂覆聚氨酯胶黏剂的316L不锈钢基材浸泡于浓度为10mM的还原型谷胱甘肽溶液(GSH)中,30min后参考标准GB/T23989-2009测试胶黏剂的擦除特性,溶剂选用丙酮。
实施例1-4为低活性聚酯多元醇的制备
实施例1
聚酯多元醇A的制备
将11.81kg丁二酸、10.36kg 1,4-丁二醇混合均匀,升温至150℃恒温1.0h;继续升温至175℃,恒温反应1.0h;加入3.76kg 1,1-二硫代二丙-2-醇,反应1.0h;将温度升至220℃加入2.59g钛酸四异丙酯,反应1.0h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇A,其酸值为0.01mg KOH/g、羟值为56.1mg KOH/g。
实施例2
聚酯多元醇B的制备
将10.01kg丁二酸酐、9.01kg 1,4-丁二醇混合均匀,升温至140℃恒温1.5h;继续升温至180℃,恒温反应0.5h;加入6.01kg 1,1-二硫代二丙-2-醇,反应1.0h;将温度升至230℃加入1.00g钛酸四异丙酯,反应0.5h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇B,其酸值为0.1mg KOH/g、羟值为149.6mg KOH/g。
实施例3
聚酯多元醇C的制备
将14.61kg己二酸、15.36kg 1,6-己二醇混合均匀,升温至160℃恒温0.5h;继续升温至180℃,恒温反应0.75h;加入1.50kg 1,1-二硫代二丙-2-醇,反应0.75h;将温度升至210℃加入5.35g钛酸正丁酯,反应0.75h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇C,其酸值为2.5mg KOH/g、羟值为37.4mg KOH/g。
实施例4
聚酯多元醇D的制备
将14.61kg己二酸、10.64kg 1,6-己二醇混合均匀,升温至145℃恒温1.5h;继续升温至170℃,恒温反应0.75h;加入7.51kg 1,1-二硫代二丙-2-醇,反应0.50h;将温度升至210℃加入9.83g钛酸正丁酯,反应0.75h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇D,其酸值为10.0mg KOH/g、羟值为11.2mg KOH/g。
对比例1-5为常规聚酯多元醇的制备
对比例1
聚酯多元醇E的制备
将11.81kg丁二酸、10.36kg 1,4-丁二醇混合均匀,升温至150℃恒温1.0h;继续升温至175℃,恒温反应1.0h;将温度升至220℃加入2.22g钛酸四异丙酯,反应1.0h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇E,其酸值为0.01mg KOH/g、羟值为56.1mg KOH/g。
对比例2
聚酯多元醇F的制备
将10.01kg丁二酸酐、9.01kg 1,4-丁二醇混合均匀,升温至150℃恒温1.0h;继续升温至175℃,恒温反应1.0h;将温度升至220℃加入1.90g钛酸四异丙酯,反应1.0h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇F,其酸值为0.1mg KOH/g、羟值为149.6mg KOH/g。
对比例3
聚酯多元醇G的制备
将11.81kg丁二酸、10.36kg 1,4-丁二醇混合均匀,升温至150℃恒温1.0h;继续升温至175℃,恒温反应1.0h;加入3.16kg 1,1-二硫代二甲醇,反应1.0h;将温度升至220℃加入2.53g钛酸四异丙酯,反应1.0h,开启真空至-0.090MPa,除去反应产物水和多余的醇单体,待酸值和羟值合格后,降温出料即可得到聚酯多元醇G,其酸值为0.01mg KOH/g、羟值为56.1mg KOH/g。
应用例1-10
双组分聚氨酯胶粘剂的制备
将低活性聚酯多元醇与多异氰酸酯化合物按照比例混合均匀,脱除气泡,将胶粘剂均匀的涂覆于PVC基材表面,记录聚氨酯胶粘剂的固化时间。
表应用例1-10热塑性聚氨酯弹性体的配方表
性能测试
聚酯多元醇反应活性
根据上述方法测试实施例和对比例聚酯多元醇的反应活性,结果如下表所示。从表中可以看出,实施例制备的聚酯多元醇与MDI反应体系粘度到达20000cP的时间均长于对比例聚酯多元醇,说明实施例制备聚酯多元醇与MDI的反应速率较慢;同时,使用伯羟基的含硫多元醇制备的聚酯多元醇反应活性也高于使用非伯羟基多元醇制备聚酯多元醇的反应活性。综上,可说明非伯羟基多元醇的引入可有效降低聚酯多元醇的反应活性。
表实施例和对比例制备聚酯多元醇反应活性
双组分聚氨酯胶粘剂性能
利用实施例和对比例聚酯多元醇制备双组分聚氨酯胶粘剂的固化时间和易清理特性数据如下表所示,其中PU-A~PU-D的多元醇原料为本发明的低活性聚酯多元醇。从表中可以看出,使用本发明低活性聚酯多元醇配置的双组分胶粘剂在常温下固化时间长,可操作时间较长,说明使用非伯羟基含硫多元醇制备的聚酯多元醇反应活性较低;同时,对比数据可发现采用本发明制备的含硫聚酯多元醇制备的聚氨酯胶粘剂在经过GSH处理后,易于清理,这主要是因为二硫键在GSH作用下可发生断键形成巯基,使胶粘剂的交联网络部分被破坏,更易于被清理。
表实施例和对比例制聚氨酯胶粘剂的性能
Claims (10)
1.一种低反应活性聚酯多元醇,由以下组分组成:
A)二元酸/酸酐:100摩尔份;
B)伯羟基多元醇:90-150摩尔份,优选为100-130摩尔份;
C)非伯羟基含硫多元醇:1-50摩尔份,优选为10-40摩尔份。
2.如权利要求1所述的低反应活性聚酯多元醇,其特征在于,所述组分A中二元酸选自碳原子数为2-20个的脂肪族二元羧酸或芳香族二元羧酸,所述酸酐选自碳原子数为4-20个的脂肪族酸酐或芳香族酸酐;优选地,所述二元酸选自丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二碳二元酸、呋喃二甲酸、邻苯二甲酸、间苯二甲酸或对苯二甲酸中的一种或多种,所述二元酸更优选为丁二酸和/或己二酸;所述酸酐选自丁二酸酐、戊二酸酐、己二酸酐、马来酸酐、四氢苯酐、六氢苯酐或邻苯二甲酸酐中的一种或多种,所述酸酐更优选为丁二酸酐。
3.如权利要求1或2所述的低反应活性聚酯多元醇,其特征在于,所述组分B伯羟基多元醇选自碳原子数为2-20个的多元醇,且多元醇上羟基均为伯羟基;优选地,所述组分B选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、十二碳二元醇、1,5-戊二醇、1,4-环己烷二甲醇、甘油、季戊四醇中的一种或多种;更优选地,所述组分B选自1,4-丁二醇、1,6-己二醇中的一种或多种。
4.如权利要求1-3任一项所述的低反应活性聚酯多元醇,其特征在于,所述组分C非伯羟基含硫多元醇选自1,1-二硫代二丙-2-醇、3,3-二硫代二丁-2-醇、1,1-三硫代二丁-2-醇、4,5-二羟基-1,2-二噻烷、3,4-二羟基-1,2-二噻烷、1,2,7,8-四羟基-4,5,10,11-四硫环十二烷中的一种或多种;优选地,所述组分C为1,1-二硫代二丙-2-醇。
5.如权利要求1-4任一项所述的低反应活性聚酯多元醇,其特征在于,所述聚酯多元醇的酸值为0.01-10.00mg KOH/g,羟值为10-200mg KOH/g;优选地,所述聚酯多元醇的酸值为0.03-5.00mg KOH/g,所述聚酯多元醇的羟值为30-150mg KOH/g;更优选地,所述聚酯多元醇的酸值为0.05-2.00mg KOH/g,所述聚酯多元醇的羟值为56-112mg KOH/g。
6.如权利要求1-5任一项所述的低反应活性聚酯多元醇的制备方法,其特征在于,包含如下步骤:1)在惰性气体存在下,将所述组分A和组分B混合后,在140-160℃下反应0.5h-1.5h;2)升温至170-180℃下反应0.5h-1.0h,加入组分C,继续反应0.5-1.0h;3)升温至210-230℃,任选地加入催化剂反应后,再在真空下继续反应至体系的酸值为0.01-10.00mgKOH/g,且羟值为10-200mg KOH/g,得到所述聚酯多元醇。
7.如权利要求6所述的制备方法,其特征在于,以所述组分A)、组分B)和组分C)的总质量计,所述催化剂的用量为0-500ppm,优选为40-300ppm。
8.如权利要求6或7所述的制备方法,其特征在于,所述催化剂选自钛类催化剂、锡类催化剂或锑类催化剂中的一种或多种;所述钛类催化剂选自钛酸正丁酯、钛酸四异丙酯或二氧化钛;所述锡类催化剂选自二月桂酸二丁基锡、辛酸亚锡或氯化亚锡;所述锑类催化剂选自醋酸锑、三氧化二锑或乙二醇锑。
9.一种双组分聚氨酯胶粘剂,所述聚氨酯胶粘剂由以下组分组成:
主剂:如权利要求1-5任一项所述的低反应活性聚酯多元醇或如权利要求6-8任一项所述的制备方法制备的低反应活性聚酯多元醇;
固化剂:多异氰酸酯化合物。
10.如权利要求9所述的双组份聚氨酯胶黏剂,其特征在于,所述双组分聚氨酯胶粘剂中低反应活性聚酯多元醇与多异氰酸酯化合物的质量比为1:0.1-2。
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