WO2022172879A1 - ポリエステルポリオール、ウレタンプレポリマー及びポリウレタン - Google Patents
ポリエステルポリオール、ウレタンプレポリマー及びポリウレタン Download PDFInfo
- Publication number
- WO2022172879A1 WO2022172879A1 PCT/JP2022/004518 JP2022004518W WO2022172879A1 WO 2022172879 A1 WO2022172879 A1 WO 2022172879A1 JP 2022004518 W JP2022004518 W JP 2022004518W WO 2022172879 A1 WO2022172879 A1 WO 2022172879A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dicarboxylic acid
- polyester polyol
- mass
- acid component
- urethane prepolymer
- Prior art date
Links
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 75
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004814 polyurethane Substances 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 164
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 20
- NPOAOTPXWNWTSH-UHFFFAOYSA-N 3-hydroxy-3-methylglutaric acid Chemical compound OC(=O)CC(O)(C)CC(O)=O NPOAOTPXWNWTSH-UHFFFAOYSA-N 0.000 description 23
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 150000002430 hydrocarbons Chemical group 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 14
- -1 3-hydroxy-3-methylglutaric acid 3-methylglutaric acid Chemical compound 0.000 description 12
- 150000001991 dicarboxylic acids Chemical class 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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 5
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 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 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- RUMVLFICHAFVGF-UHFFFAOYSA-N 4-methyl-3h-pyran-2,6-dione Chemical compound CC1=CC(=O)OC(=O)C1 RUMVLFICHAFVGF-UHFFFAOYSA-N 0.000 description 3
- 102000009012 HMGA Proteins Human genes 0.000 description 3
- 108010049069 HMGA Proteins Proteins 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 2
- MGICRVTUCPFQQZ-UHFFFAOYSA-N 4-methyloxane-2,6-dione Chemical compound CC1CC(=O)OC(=O)C1 MGICRVTUCPFQQZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 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
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-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
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-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
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-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
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DCBHEUHFBOSTDA-UHFFFAOYSA-N 2,3-bis(2-hydroxyethoxy)terephthalic acid Chemical compound OCCOC1=C(C(O)=O)C=CC(C(O)=O)=C1OCCO DCBHEUHFBOSTDA-UHFFFAOYSA-N 0.000 description 1
- HDMPSPHLMYRMKD-UHFFFAOYSA-N 2,7-dimethyloctane-1,8-diol Chemical compound OCC(C)CCCCC(C)CO HDMPSPHLMYRMKD-UHFFFAOYSA-N 0.000 description 1
- QSXIQLGLLBVKPF-UHFFFAOYSA-N 2,8-dimethylnonane-1,9-diol Chemical compound OCC(C)CCCCCC(C)CO QSXIQLGLLBVKPF-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 1
- GQSJKULLLUNPMA-UHFFFAOYSA-N 2-methylnonane-1,9-diol Chemical compound OCC(C)CCCCCCCO GQSJKULLLUNPMA-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- SMFZAIRMNYPZLI-UHFFFAOYSA-N 4-methyloxan-2-ol Chemical compound CC1CCOC(O)C1 SMFZAIRMNYPZLI-UHFFFAOYSA-N 0.000 description 1
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 1
- QJUGRDPUBVMMGN-UHFFFAOYSA-N CC(CC(=O)O)CC(=O)O.CC(CC(=O)O)CC(=O)O Chemical compound CC(CC(=O)O)CC(=O)O.CC(CC(=O)O)CC(=O)O QJUGRDPUBVMMGN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate 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
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
Definitions
- the present invention relates to a polyester polyol that has excellent hydrolysis resistance and that can keep the viscosity low when used in a prepolymer. It also relates to a urethane prepolymer and polyurethane using the polyester polyol.
- polyester polyols with hydroxyl groups at the molecular ends have been used as polyol components used as raw materials for paints, adhesives, foams, polyurethanes, and the like.
- polyester polyols are inferior in hydrolysis resistance, there is a problem that the surface of products using them becomes tacky or cracks occur in a relatively short period of time.
- the polyester polyol obtained by this method has a high tendency to crystallize and tends to become a highly viscous liquid or solid, resulting in a problem of reduced workability.
- the flex resistance, flexibility, low-temperature adhesiveness, etc. are inferior.
- Patent Document 1 proposes a polyester polyol using 2-methyl-1,8-octanediol and 1,9-nonanediol as diol components. Further, Patent Document 2 proposes a polyester polyol using 3-methylpentanedioic acid having a branched structure.
- polyester polyols described in Patent Documents 1 and 2 are excellent in hydrolysis resistance, the viscosity of the urethane prepolymers using them is not sufficiently low, and further improvements have been desired.
- the present invention has been made in view of the above-described conventional problems, and provides a polyester polyol that is excellent in hydrolysis resistance and can keep the viscosity low when used in a urethane prepolymer, and a urethane prepolymer using the same.
- the object is to provide polymers and polyurethanes.
- the present inventors have made various studies on improving the hydrolysis resistance of polyester polyol and reducing the viscosity of urethane prepolymers using this polyester polyol.
- 3-methylpentanedioic acid 3-methylglutaric acid
- polyester The inventors have found that the viscosity of a urethane prepolymer using a polyol is reduced, and have completed the present invention as a result of further studies.
- R 1 , R 2 , R 4 and R 5 each independently represent a divalent hydrocarbon group having 1 to 3 carbon atoms
- R 3 and R 6 Each independently represents a monovalent hydrocarbon group having 1 to 3 carbon atoms.
- the present invention it is possible to provide a polyester polyol that is excellent in hydrolysis resistance and can keep the viscosity low when used in a urethane prepolymer, and a urethane prepolymer and polyurethane using the same.
- FIG. 2 is a graph showing the area ratio of the contents of dicarboxylic acids (a1) and (a2) contained in the dicarboxylic acid component (A) obtained in Production Example 1.
- FIG. 2 is a graph showing the area ratio of the contents of dicarboxylic acids (a1) and (a2) contained in the dicarboxylic acid component (A) obtained in Production Example 1.
- the polyester polyol of the present invention is a polyester polyol obtained by reacting a dicarboxylic acid component (A) and a diol component (B), and the dicarboxylic acid component (A) is a dicarboxylic acid represented by the following general formula (I). (a1) and a dicarboxylic acid (a2) represented by the following general formula (II), wherein the content of the dicarboxylic acid (a2) in 100% by mass of the total amount of the dicarboxylic acid component (A) is 0.02 It is characterized by being ⁇ 3.00% by mass.
- R 1 , R 2 , R 4 and R 5 each independently represent a divalent hydrocarbon group having 1 to 3 carbon atoms
- R 3 and R 6 Each independently represents a monovalent hydrocarbon group having 1 to 3 carbon atoms.
- the present invention uses both the dicarboxylic acid (a1) represented by the general formula (I) and the dicarboxylic acid (a2) represented by the general formula (II) as the dicarboxylic acid component (A). It is characterized by In the production of general polyester polyols, it is common to use one kind of highly purified dicarboxylic acid as the dicarboxylic acid component. An attempt was made to combine the dicarboxylic acid (a2), which is not usually used. As a result, the inventors have found that the viscosity of the urethane prepolymer using this polyester polyol is lowered while maintaining the hydrolysis resistance of the obtained polyester polyol at a high level, and completed the present invention. The present invention will be described in detail below.
- the dicarboxylic acid component (A) contains the dicarboxylic acid (a1) represented by the general formula (I) and the dicarboxylic acid (a2) represented by the general formula (II).
- Dicarboxylic acid (a1) is a dicarboxylic acid represented by the following general formula (I).
- R 1 and R 2 in general formula (I) each independently represent a divalent hydrocarbon group having 1 to 3 carbon atoms.
- the hydrocarbon groups represented by R 1 and R 2 may be different, but from the viewpoint of ease of production, R 1 and R 2 are preferably the same hydrocarbon group.
- R 1 and R 2 a divalent hydrocarbon group having 1 to 2 carbon atoms is preferable, and a divalent hydrocarbon group having 1 carbon atom is more preferable.
- R 1 and R 2 may be linear or branched, and may have substituents such as halogen atoms and hydroxyl groups.
- R 3 in general formula (I) represents a monovalent hydrocarbon group having 1 to 3 carbon atoms. is more preferably a methyl group which is a monovalent hydrocarbon group of .
- R 3 may be linear or branched, and may have substituents such as halogen atoms and hydroxyl groups. Among these, 3-methylglutaric acid in which both R 1 and R 2 are methylene groups and R 3 is a methyl group is preferred as the dicarboxylic acid (a1) represented by the general formula (I).
- 3-Methylglutaric acid can be produced, for example, by the method described in JP-A-7-258148. Specifically, ⁇ -methyl- ⁇ -valerolactone, 2-hydroxy-4-methyltetrahydropyran and A compound selected from the group consisting of 3-methyl-1,5-pentanediol can be prepared by oxygen oxidation in the presence of an oxidation catalyst and water.
- the content of the dicarboxylic acid (a1) in 100% by mass of the total dicarboxylic acid component (A) is preferably 97.00 to 99.98% by mass.
- the content of the dicarboxylic acid (a1) is 97.00% by mass or more, various physical properties of the product made from the polyester polyol can be improved.
- the content is 99.98% by mass or less, the viscosity of the prepolymer using the polyester polyol can be lowered.
- the content of the dicarboxylic acid (a1) in 100% by mass of the total amount of the dicarboxylic acid component (A) is preferably 97.50 to 99.97% by mass, more preferably 98.00 to 99%. .96% by mass, more preferably 98.50 to 99.95% by mass.
- Dicarboxylic acid (a2) is a dicarboxylic acid represented by the following general formula (II).
- R 4 and R 5 in general formula (II) each independently represent a divalent hydrocarbon group having 1 to 3 carbon atoms.
- the hydrocarbon groups represented by R 4 and R 5 may be different, but from the viewpoint of ease of production, R 4 and R 5 are preferably the same hydrocarbon group.
- R 4 and R 5 a divalent hydrocarbon group having 1 to 2 carbon atoms is preferable, and a divalent hydrocarbon group having 1 carbon atom is more preferable.
- R 4 and R 5 may be linear or branched, and may have substituents such as halogen atoms and hydroxyl groups.
- R 6 in general formula (II) represents a monovalent hydrocarbon group having 1 to 3 carbon atoms. is more preferably a methyl group which is a monovalent hydrocarbon group of .
- R 6 may be linear or branched, and may have substituents such as halogen atoms and hydroxyl groups.
- the dicarboxylic acid (a2) represented by the general formula (II) is 3-hydroxy-3-methylglutaric acid in which both R 4 and R 5 are methylene groups and R 6 is a methyl group. is preferred.
- a method for producing 3-hydroxy-3-methylglutaric acid includes, for example, the method described in JP-A-60-190735.
- the dicarboxylic acid (a1) is 3-methylglutaric acid
- the dicarboxylic acid (a2) is 3- Hydroxy-3-methylglutaric acid is preferred.
- the dicarboxylic acid (a1) is produced using the dicarboxylic acid (a2) as a raw material (for example, by dehydrating and hydrogenating 3-hydroxy-3-methylglutaric acid 3-methylglutaric acid) to obtain a mixture of dicarboxylic acid (a1) and dicarboxylic acid (a2), and by purifying this mixture, the amount of dicarboxylic acid (a1) and dicarboxylic acid (a2) It becomes possible to adjust the ratio, which facilitates the preparation of the dicarboxylic acid component (A).
- the content of the dicarboxylic acid (a2) in 100% by mass of the total amount of the dicarboxylic acid component (A) is 0.02 to 3.00% by mass. If the content of the dicarboxylic acid (a2) is less than 0.02% by mass, the viscosity of the urethane prepolymer obtained by reacting the polyester polyol with the polyisocyanate compound cannot be reduced. On the other hand, when the content exceeds 3.00% by mass, yellowing occurs in the obtained polyester polyol. From these viewpoints, the content of the dicarboxylic acid (a2) in 100% by mass of the total amount of the dicarboxylic acid component (A) is preferably 0.03 to 2.50% by mass, more preferably 0.04 to 2.0%. 0.00% by mass, more preferably 0.05 to 1.50% by mass.
- the dicarboxylic acid component (A) used in the present invention may contain dicarboxylic acids other than the dicarboxylic acid (a1) and the dicarboxylic acid (a2).
- Other dicarboxylic acids are not particularly limited, but low-molecular-weight dicarboxylic acids are more preferred.
- low-molecular-weight dicarboxylic acids examples include aliphatic dicarboxylic acids such as succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; ; phthalic acid, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, and the like. These dicarboxylic acids may be used individually by 1 type, and may be used in mixture of 2 or more types. In the present invention, a polycarboxylic acid having a functionality of 3 or more may be used, and when a polycarboxylic acid having a functionality of 3 or more is used, it is treated as a dicarboxylic acid component (A).
- aliphatic dicarboxylic acids such as succinic acid,
- the content of other dicarboxylic acids contained in 100% by mass of the total dicarboxylic acid component (A) is preferably 20.0% by mass or less, more preferably 10.0% by mass or less, and still more preferably by mass 5.0% or less.
- the content of the other dicarboxylic acid is equal to or less than the above upper limit, it becomes easier to obtain the effect based on the dicarboxylic acid component (a1).
- the content of the dicarboxylic acid component (a2) relative to 100 parts by mass of the dicarboxylic acid component (a1) is preferably 3.00. It is not more than 2.00 parts by mass, and more preferably not more than 2.00 parts by mass. The closer the content of the dicarboxylic acid component (a2) is to the upper limit, the easier it is to obtain the effect based on the dicarboxylic acid component (a2).
- diol component (B) used in the present invention examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol and 1,3-butanediol.
- the polyester polyol of the present invention contains an aromatic ring-containing diol such as 1,4-bis( ⁇ -hydroxyethoxy)benzene and bis( ⁇ -hydroxyethoxy)terephthalate, as long as it does not impair the gist of the invention. You may have In addition, trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, and other trifunctional or higher polyols may be contained.
- aromatic ring-containing diol such as 1,4-bis( ⁇ -hydroxyethoxy)benzene and bis( ⁇ -hydroxyethoxy)terephthalate, as long as it does not impair the gist of the invention. You may have In addition, trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol, and other trifunctional or higher polyols may be contained.
- the polyester polyol of the present invention preferably has a number average molecular weight of 300 to 30,000.
- the mechanical properties such as strength of the polyurethane produced using the polyester polyol are improved.
- the number average molecular weight of the polyester polyol is 30,000 or less, the low-temperature properties and flexibility of the polyurethane produced using the polyester polyol are improved.
- the number average molecular weight of the polyester polyol is more preferably 700 to 20,000, even more preferably 1,000 to 10,000.
- the number average molecular weight of the polyester polyol refers to the value obtained by the method described in Examples.
- the number of hydroxyl groups in one polyester polyol molecule varies depending on the application, but it is preferably two or more per molecule. Yes, and has versatility.
- the method for producing the polyester polyol of the present invention is not particularly limited, and it can be produced by a known polycondensation method.
- the product can be produced by further polycondensation reaction at high temperature in the presence of a polycondensation catalyst under vacuum.
- a known catalyst can be used, for example, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium Titanium compounds such as titanium; Tin compounds such as di-n-butyltin oxide, di-n-butyltin dilaurate, and dibutyltin diacetate; Combinations of acetates such as magnesium, calcium, and zinc with antimony oxide or the above titanium compounds, and the like. be able to.
- These polycondensation catalysts are preferably present in an amount of 5 to 500 ppm relative to the total amount of the dicarboxylic acid component (A) and the diol component (B).
- the urethane prepolymer of the present invention is obtained by reacting the polyester polyol of the present invention with a polyisocyanate compound, and the viscosity can be kept low compared to urethane prepolymers produced from similar raw materials. Therefore, the degree of freedom in subsequent blending is improved, and for example, it is possible to improve the dispersibility of pigments and the like. Additionally, the low viscosity of the urethane prepolymer improves workability in paint, adhesive and foam applications. Moreover, the polyurethane of the present invention uses the polyester polyol or urethane prepolymer of the present invention, and is excellent in hydrolysis resistance due to the properties of the polyester polyol.
- the polyisocyanate compound used in the present invention is not particularly limited as long as it has two or more isocyanate groups in one molecule.
- Aromatic polyisocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanatomethyl, etc.
- Alicyclic polyisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate; carbodiimide-modified isocyanate compounds and isocyanurate-modified isocyanate compounds of these isocyanate compounds ; and the like.
- These polyisocyanate compounds may be used singly or in combination of two or more.
- aromatic polyisocyanate and alicyclic polyisocyanate are preferred from the viewpoint of improving various physical properties such as strength of the resulting polyurethane, and liquid tolylene diisocyanate (TDI) from the viewpoint of lowering viscosity.
- TDI liquid tolylene diisocyanate
- IPDI isophorone diisocyanate
- the urethane prepolymer of the present invention is obtained by reacting the polyester polyol of the present invention with a polyisocyanate compound, and can keep the viscosity lower than that of urethane prepolymers produced from the same starting materials.
- the viscosity at 60° C. is preferably 4,000 mPa ⁇ s or less, more preferably 3,500 mPa ⁇ s or less, and even more preferably 1,500 mPa ⁇ s or less.
- the viscosity at 60° C. of the urethane prepolymer is equal to or less than the above upper limit, workability is improved in applications such as paints, adhesives and foams.
- the viscosity of the urethane prepolymer at 60°C can be measured by the method described in Examples.
- the urethane prepolymer can be produced by mixing optional components such as the polyester polyol of the present invention, the polyisocyanate compound, and a plasticizer used as necessary.
- Mixing devices are not particularly limited, and examples include rolls, kneaders, pressure kneaders, Banbury mixers, horizontal mixers (e.g., Loedige mixers), vertical mixers (e.g., planetary mixers, etc.), extruders, universal stirring. machine etc.
- the optional components include plasticizers, cross-linking agents, fillers, cross-linking accelerators, cross-linking aids, tackifiers, anti-aging agents, foaming agents, processing aids, adhesion imparting agents, inorganic fillers, organic Fillers, crystal nucleating agents, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, flame retardants, flame retardant aids (antimony oxide, etc.), anti-blooming agents, release agents, thickeners, antioxidants Additives such as agents and conductive agents may be contained.
- the content of the optional component in the urethane prepolymer is not particularly limited, but is preferably 50% by mass or less, more preferably 20% by mass or less, and still more preferably 5% by mass or less.
- the method for producing the polyurethane of the present invention is not particularly limited, but it is preferably obtained by polymerizing the raw materials described above through a urethanization reaction using a known prepolymer method or one-shot method. More specifically, in the absence of a solvent substantially, the above-described components are blended in a predetermined ratio and melt-mixed using a single-screw or multi-screw extruder by melt polymerization. and a method of producing by polymerization by a prepolymer method in the presence of a solvent. In addition, you may perform melt polymerization continuously. For example, the obtained polyurethane may be pelletized and then molded into a sheet-like molding by various molding methods such as extrusion molding, injection molding, blow molding, and calender molding.
- the content of the dicarboxylic acids (a1) and (a2) in the total amount of the dicarboxylic acid component (A) uses the peak areas (%) of the dicarboxylic acids (a1) and (a2) obtained by the following LC measurement. , was obtained from the following formula.
- ⁇ Viscosity of urethane prepolymer> The viscosities at 60° C. of the urethane prepolymers obtained in Examples and Comparative Examples were measured with a Brookfield LVDV-II viscometer.
- FIG. 1 shows the results of LC measurement performed on the obtained dicarboxylic acid component (A).
- HMGA indicates 3-hydroxy-3-methylglutaric acid (dicarboxylic acid (a2))
- MGA indicates 3-methylglutaric acid (dicarboxylic acid (a1)).
- Example 1 [Synthesis of polyester polyol] As a dicarboxylic acid component (A) [1 mol], 146 g of 3-methylglutaric acid obtained in Production Example 1 was prepared. The content of 3-methylglutaric acid [dicarboxylic acid (a1)] in the dicarboxylic acid component (A) was 98.72% by mass, and 3-hydroxy-3-methylglutaric acid [dicarboxylic acid (a2)] was 1.28% by mass. Furthermore, 177 g (1.5 mol) of 3-methyl-1,5-pentanediol was prepared as the diol component (B) and charged into the reactor. Then, the mixture was heated to 200° C.
- a urethane prepolymer was produced in the same manner as in Example 1 by using a polyisocyanate compound with the formulation shown in Table 2, and the viscosity was measured. Table 2 shows the results.
- the polyester polyols obtained in Examples 1 to 5 were low-viscosity liquids at 20°C.
- each component is represented by the following abbreviations.
- MGA 3-methylglutaric acid
- HMGA 3-hydroxy-3-methylglutaric acid
- MPD 3-methyl-1,5-pentanediol
- TDI tolylene diisocyanate
- IPDI isophorone diisocyanate
- BD 1,4-butanediol ADA: adipine acid
- the polyester of the example synthesized using the dicarboxylic acid component (A) containing both the dicarboxylic acid (a1) and the dicarboxylic acid (a2) and containing a specific amount of the dicarboxylic acid (a2) The polyol has hydrolysis resistance equivalent to that of a polyester polyol having a similar structure, and can keep the viscosity of the urethane prepolymer low.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
しかしながら、この方法により得られたポリエステルポリオールは結晶化傾向が高く、高粘度の液体又は固体となりやすいため作業性が低下するという問題があった。また-20℃程度の低温雰囲気下で使用すると耐屈曲性、柔軟性、及び低温接着性等が劣るという問題もあった。
[1]ジカルボン酸成分(A)とジオール成分(B)とを反応させたポリエステルポリオールであり、前記ジカルボン酸成分(A)が、下記一般式(I)で表されるジカルボン酸(a1)と、下記一般式(II)で表されるジカルボン酸(a2)とを含み、
前記ジカルボン酸成分(A)全量100質量%中の前記ジカルボン酸(a2)の含有量が0.02~3.00質量%であることを特徴とするポリエステルポリオール。
[3]前記一般式(I)及び(II)中のR1、R2、R4及びR5がいずれもメチレン基である、前記[1]又は[2]に記載のポリエステルポリオール。
[4]前記[1]~[3]のいずれかに記載のポリエステルポリオールとポリイソシアネート化合物とを反応させたウレタンプレポリマー。
[5]前記[1]~[3]のいずれかに記載のポリエステルポリオール又は前記[4]に記載のウレタンプレポリマーを用いたポリウレタン。
本発明のポリエステルポリオールは、ジカルボン酸成分(A)とジオール成分(B)とを反応させたポリエステルポリオールであり、前記ジカルボン酸成分(A)が、下記一般式(I)で表されるジカルボン酸(a1)と、下記一般式(II)で表されるジカルボン酸(a2)とを含み、前記ジカルボン酸成分(A)全量100質量%中の前記ジカルボン酸(a2)の含有量が0.02~3.00質量%であることを特徴とするものである。
本発明においてジカルボン酸成分(A)は、前記一般式(I)で表されるジカルボン酸(a1)と、前記一般式(II)で表されるジカルボン酸(a2)とを含むものである。
〔ジカルボン酸(a1)〕
ジカルボン酸(a1)は、下記一般式(I)で表されるジカルボン酸である。
なお、R1及びR2は直鎖状でも分岐鎖状であってもよく、また、ハロゲン原子、水酸基等の置換基を有していてもよい。
なお、R3は直鎖状でも分岐鎖状であってもよく、また、ハロゲン原子、水酸基等の置換基を有していてもよい。
これらの中でも、一般式(I)で表されるジカルボン酸(a1)としては、R1及びR2がいずれもメチレン基であり、R3がメチル基である3-メチルグルタル酸が好ましい。
これらの観点から、ジカルボン酸成分(A)の全量100質量%中におけるジカルボン酸(a1)の含有量は、好ましくは97.50~99.97質量%であり、より好ましくは98.00~99.96質量%であり、更に好ましくは98.50~99.95質量%である。
なお、R4及びR5は直鎖状でも分岐鎖状であってもよく、また、ハロゲン原子、水酸基等の置換基を有していてもよい。
なお、R6は直鎖状でも分岐鎖状であってもよく、また、ハロゲン原子、水酸基等の置換基を有していてもよい。
これらの中でも、一般式(II)で表されるジカルボン酸(a2)としては、R4及びR5がいずれもメチレン基であり、R6がメチル基である3-ヒドロキシ-3-メチルグルタル酸が好ましい。
これらの観点から、ジカルボン酸成分(A)の全量100質量%中におけるジカルボン酸(a2)の含有量は、好ましくは0.03~2.50質量%であり、より好ましくは0.04~2.00質量%であり、更に好ましくは0.05~1.50質量%である。
本発明において用いるジカルボン酸成分(A)は、前記ジカルボン酸(a1)及びジカルボン酸(a2)以外にその他のジカルボン酸を含んでもよい。
その他のジカルボン酸に特に制限はないが、低分子のジカルボン酸がより好ましい。
低分子のジカルボン酸としては、例えば、コハク酸、メチルコハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸;フタル酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸等が挙げられる。これらのジカルボン酸は1種を単独で用いてもよく、2種以上を混合して用いてもよい。
なお、本発明においては、3官能以上のポリカルボン酸を用いてもよく、3官能以上のポリカルボン酸を用いた場合はジカルボン酸成分(A)として扱う。
なお、本発明において、その他のジカルボン酸を含む場合、及び含まない場合のいずれにおいても、ジカルボン酸成分(a1)100質量部に対する前記ジカルボン酸成分(a2)の含有量は、好ましくは3.00質量部以下であり、より好ましくは2.00質量部以下である。ジカルボン酸成分(a2)の含有量が前記上限値に近いほどジカルボン酸成分(a2)に基づく効果を得やすくなる。
本発明に用いるジオール成分(B)としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、1,3-プロパンジオール、2-メチル-1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2-メチル-1,4-ブタンジオール、1,5-ペンタンジオール、3-メチル-1,5-ペンタンジオール、1,6-ヘキサンジオール、2-メチル-1,8-オクタンジオール、2,7-ジメチル-1,8-オクタンジオール、1,9-ノナンジオール、2-メチル-1,9-ノナンジオール、2,8-ジメチル-1,9-ノナンジオール、1,10-デカンジオール、2,2-ジエチル-1,3-プロパンジオール、2-ブチル-2-エチル-1,3-プロパンジオール等の脂肪族ジオール;1,4-シクロヘキサンジオール、シクロヘキサンジメタノール、3(又は4),8(又は9)-ジヒドロキシトリシクロ[5.2.1.02,6]デカン等の脂環式ジオール等が挙げられるが、これらの中でも脂肪族ジオールが好ましい。これらのジオールは1種を単独で使用してもよいし、2種以上を混合して用いてもよい。
本発明のポリエステルポリオールの数平均分子量は300~30,000であることが好ましい。ポリエステルポリオールの数平均分子量が300以上であると、ポリエステルポリオールを用いて製造したポリウレタンの強度等の力学的特性が向上する。一方、ポリエステルポリオールの数平均分子量が30,000以下であると、ポリエステルポリオールを用いて製造したポリウレタンの低温特性や柔軟性が良好になる。これらの観点からポリエステルポリオールの数平均分子量は700~20,000であることがより好ましく、1,000~10,000であることが更に好ましい。
なお、本発明においてポリエステルポリオールの数平均分子量は実施例に記載の方法により求めた値を指す。
本発明においてポリエステルポリオール1分子中の水酸基の数は、用途により異なるが、1分子あたり2個以上であることが好ましく、2~3個の範囲にあればポリエステルは最も多くの用途に使用可能であり、汎用性を有する。
本発明のポリエステルポリオールの製造方法には特に制限はなく、公知の重縮合する方法により製造することができる。
例えば、前記ジカルボン酸(a1)及びジカルボン酸(a2)を含むジカルボン酸成分(A)と、前記ジオール成分(B)とを所定の割合で仕込み、エステル化又はエステル交換反応を行い、得られる反応生成物を重縮合触媒の存在下に高温、真空下で更に重縮合反応させることにより製造することができる。
なお、ポリエステルポリオールの製造に使用される重縮合触媒としては、公知の触媒を使用することができ、例えば、テトラメトキシチタン、テトラエトキシチタン、テトラ-n-プロポキシチタン、テトライソプロポキシチタン、テトラブトキシチタン等のチタン化合物;ジ-n-ブチルスズオキサイド、ジ-n-ブチルスズジラウレート、ジブチルスズジアセテート等のスズ化合物;マグネシウム、カルシウム、亜鉛等の酢酸塩と酸化アンチモン又は上記チタン化合物との組み合わせ等を挙げることができる。
これらの重縮合触媒は、ジカルボン酸成分(A)及び前記ジオール成分(B)の全量に対し5~500ppmであることが好ましい。
本発明のウレタンプレポリマーは、本発明のポリエステルポリオールとポリイソシアネート化合物とを反応させたものであり、同様の原料から製造したウレタンプレポリマーと比較して粘度を低く抑えることができる。よって、その後の配合の自由度が向上し、例えば顔料等の分散性を良好にすることが可能になる。更に、ウレタンプレポリマーの粘度を低く抑えることによって、塗料、接着剤及びフォームの用途において作業性が向上する。
また、本発明のポリウレタンは本発明のポリエステルポリオール又はウレタンプレポリマーを用いたものであり、ポリエステルポリオールの特性に起因して耐加水分解性に優れる。
本発明に用いるポリイソシアネート化合物としては、1分子中に2個以上のイソシアネート基を有する限り特に制限はなく、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、1,4-フェニレンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、トリジンジイソシアネート、1,5-ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等の芳香族ポリイソシアネート;ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアナートメチルなどの脂肪族ポリイソシアネート;トランスシクロヘキサン-1,4-ジイソシアネート、イソホロンジイソシアネート、ビス(イソシアネートメチル)シクロヘキサン、ジシクロヘキシルメタンジイソシアネート等の脂環式ポリイソシアネート;これらイソシアネート化合物のカルボジイミド変性イソシアネート化合物、イソシアヌレート変性イソシアネート化合物;等が挙げられる。これらのポリイソシアネート化合物は1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明のウレタンプレポリマーは、本発明のポリエステルポリオールとポリイソシアネート化合物とを反応させたものであって同様の原料から製造したウレタンプレポリマーと比較して粘度を低く抑えることができるが、具体的には60℃における粘度が、4,000mPa・s以下であることが好ましく、3,500mPa・s以下であることがより好ましく、1,500mPa・s以下であることが更に好ましい。ウレタンプレポリマーの60℃における粘度が前記上限値以下であると、塗料、接着剤及びフォームの用途において作業性が向上する。
なお、ウレタンプレポリマーの60℃における粘度は実施例に記載の方法で測定することができる。
ウレタンプレポリマーは、本発明のポリエステルポリオール、前記ポリイソシアネート化合物、及び必要に応じて用いる可塑剤等の任意成分を混合することにより製造できる。
混合装置は特に制限はなく、例えば、ロール、ニーダー、加圧ニーダー、バンバリーミキサー、横型ミキサー(例えば、レーディゲミキサー等)、縦型ミキサー(例えば、プラネタリーミキサー等)、押出し機、万能撹拌機等が挙げられる。
ウレタンプレポリマー中の任意成分の含有量に特に制限はないが、好ましくは50質量%以下であり、より好ましくは20質量%以下であり、更に好ましくは5質量%以下である。
本発明のポリウレタンの製造方法に特に制限はないが、前述の各原料を用いて公知のプレポリマー法又はワンショット法を用いたウレタン化反応によって重合することにより得ることが好ましい。
より具体的には、実質的に溶剤の不存在下で、上述した各成分を所定の比率で配合して単軸又は多軸スクリュー型押出機を用いて溶融混合しながら溶融重合により製造する方法や、溶剤存在下でプレポリマー法により重合にて製造する方法等が挙げられる。なお、溶融重合は連続的に行ってもよい。
得られたポリウレタンは、例えば、ペレット化した後、押出成形法、射出成形法、ブロー成形法、カレンダー成形法等の各種の成形法によりシート状の成形体に成形してもよい。
なお、実施例及び比較例においてジカルボン酸成分(A)全量中の前記ジカルボン酸(a1)及び(a2)の含有量、ポリエステルポリオールの数平均分子量は下記方法で測定した。
また、ポリエステルポリオールの耐加水分解性、及びプレポリマーの粘度の評価は下記の方法により行った。
ジカルボン酸成分(A)全量中の前記ジカルボン酸(a1)及び(a2)の含有量は、以下のLC測定で得られた前記ジカルボン酸(a1)及び(a2)のピーク面積(%)を用い、以下の式から求めた。
ジカルボン酸(a1)の含有量(質量%)=
ジカルボン酸(a1)のピーク面積(%)×100/(ジカルボン酸(a1)のピーク面積(%)+ジカルボン酸(a2)のピーク面積(%))
ジカルボン酸(a2)の含有量(質量%)=
ジカルボン酸(a2)のピーク面積(%)×100/(ジカルボン酸(a1)のピーク面積(%)+ジカルボン酸(a2)のピーク面積(%))
株式会社島津製作所製HPLC Prominenceを用い、以下の条件で測定した面積値を用いた。
カラム :L-columnODS(一般財団法人 化学物質評価機構(CERI)製、4.6×150mm)
流量 :1.0mL/min
注入量 :5μL(試料濃度:12mg/mL、溶媒:アセトニトリル)
検出器 :UV(220nm)
カラム温度 :40℃
溶離液A :0.1質量%リン酸水溶液
溶離液B :アセトニトリル
グラジエント:下記表1の条件
保持時間(HMGA):2.3min
保持時間(MGA) :3.6min
実施例及び比較例で得られたポリエステルポリオールの水酸基価に基づいて計算により求めた。なお、水酸基価の測定はJIS K1557-1に記載のフタル化法により測定した。
実施例及び比較例で得られたポリエステルポリオール0.5gを100℃の熱水10ml中に7日間放置した。次いで、JIS K1557-5:2007に準じて水及びポリエステルポリオールの酸価を測定し、両者を合計したものを酸性値として耐加水分解性の指標とした。酸性値が小さいほど耐加水分解性が優れていることを示す。
実施例及び比較例で得られたウレタンプレポリマーの60℃における粘度を、ブルックフィールド社B型粘度計LVDV-IIで測定した。
<製造例1:3-メチルグルタル酸の合成>
下記の方法にしたがって、3-ヒドロキシ-3-メチルグルタル酸を製造した後、これを原料に4-メチル-3,6-ジヒドロ-2H-ピラン-2,6-ジオンを製造した。次いでこれを原料に3-メチルグルタル酸を製造した。
まず特開昭60-190735号公報に記載の方法にしたがって、3-ヒドロキシ-3-メチルグルタル酸を製造した。得られた3-ヒドロキシ-3-メチルグルタル酸300gを冷却器を備えた三ツ口フラスコに仕込み、塩化アセチル600mLを加えた後、60℃に加熱して5時間のアセチル化反応を行った。冷却後回収した反応物は濾別した後、キシレンで洗浄を行った。その後、反応物を再度三ツ口フラスコに仕込み、600mLのキシレンを加え150℃に加熱、還流下5時間の脱アセチル化反応を行い4-メチル-3,6-ジヒドロ-2H-ピラン-2,6-ジオンを製造した。反応物は反応液の冷却による晶析によって分離取得した。
反応液から濾別により触媒を除去した後、ロータリーエバポレーターで溶媒を除去し3-メチルグルタル酸無水物を得た。
更に、得られた3-メチルグルタル酸無水物128gを冷却器を備えた三ツ口フラスコに水18g、トルエン500mLと共に仕込んだ。これを70℃にて加熱し、撹拌を5時間行うことで溶媒中での加水分解により3-メチルグルタル酸を得た。得られた反応物は反応液の冷却による晶析によって分離取得した。得られたジカルボン酸成分(A)中の3-ヒドロキシ-3-メチルグルタル酸〔ジカルボン酸(a2)〕の含有量は1.28質量%であった。
なお、得られたジカルボン酸成分(A)について行ったLC測定の結果を図1に示す。図1中、HMGAは3-ヒドロキシ-3-メチルグルタル酸(ジカルボン酸(a2))を示し、MGAは3-メチルグルタル酸(ジカルボン酸(a1))を示す。
<実施例1>
〔ポリエステルポリオールの合成〕
ジカルボン酸成分(A)〔1モル〕として、前記製造例1で得られた3-メチルグルタル酸146gを準備した。なお、ジカルボン酸成分(A)中の3-メチルグルタル酸〔ジカルボン酸(a1)〕の含有量は98.72質量%であり、3-ヒドロキシ-3-メチルグルタル酸〔ジカルボン酸(a2)〕の含有量は1.28質量%であった。
更にジオール成分(B)として3-メチル-1,5-ペンタンジオール177g(1.5モル)を準備し、これらを反応器に仕込んだ。次いで、常圧下、窒素雰囲気中で200℃に加熱し、生成する水を系外に留去しながらエステル化反応を行った。
生成した水の留出が少なくなった時点で、テトライソプロポキシチタン5mgを添加し、真空ポンプで200~100mmHgに減圧しながら反応を続け、水酸基価56.5KOHmg/g、酸価0.05KOHmg/g及び数平均分子量1,986のポリエステルポリオールを得た。
得られたポリエステルポリオールの耐加水分解性を前記の方法に従って測定した。結果を表2に示す。
得られたポリエステルポリオール50g(0.025mol)を三ツ口フラスコに秤量した。次いで、三ツ口フラスコにバキュームスターラー、メカニカル撹拌機をセットした後、80℃の油浴に浸漬し、真空ポンプにより減圧しながらポリエステルポリオールを脱水した。
1時間の脱水後、窒素雰囲気下においてトリレンジイシシアネート(株式会社東ソー製「コロネートT-65」)8.77g(0.05mol)を投入し、80℃で10分間撹拌混合した。その後、60℃に温度を下げ窒素雰囲気下で2時間撹拌を継続した。
得られたウレタンプレポリマーの粘度を、上記の方法で測定することにより評価した。結果を表2に示す。
表2に示すジカルボン酸成分(A)及びジオール成分(B)を用い、実施例1と同様にポリエステルポリオールを製造し、数平均分子量の計算及び耐加水分解性の評価を行った。結果を表2に示す。
なお、ジカルボン酸成分(A)中のジカルボン酸(a1)及びジカルボン酸(a2)の量比は、表2に記載の精製回数(具体的には、加熱トルエンからの再結晶の回数)により調整した。
また、表2に示す配合でポリイソシアネート化合物を用いることにより実施例1と同様にウレタンプレポリマーを製造し、粘度を測定した。結果を表2に示す。
なお、実施例1~5で得られたポリエステルポリオールは20℃で低粘度の液体であった。
MGA :3-メチルグルタル酸
HMGA :3-ヒドロキシ-3-メチルグルタル酸
MPD :3-メチル-1,5-ペンタンジオール
TDI :トリレンジイソシアネート
IPDI :イソホロンジイソシアネート
BD :1,4-ブタンジオール
ADA :アジピン酸
Claims (5)
- 前記ジカルボン酸成分(a1)100質量部に対する前記ジカルボン酸成分(a2)の含有量が3.00質量部以下である、請求項1に記載のポリエステルポリオール。
- 前記一般式(I)及び(II)中のR1、R2、R4及びR5がいずれもメチレン基である、請求項1又は2に記載のポリエステルポリオール。
- 請求項1~3のいずれかに記載のポリエステルポリオールとポリイソシアネート化合物とを反応させたウレタンプレポリマー。
- 請求項1~3のいずれかに記載のポリエステルポリオール又は請求項4に記載のウレタンプレポリマーを用いたポリウレタン。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280013784.4A CN116917372A (zh) | 2021-02-10 | 2022-02-04 | 聚酯多元醇、氨基甲酸酯预聚物及聚氨酯 |
EP22752703.3A EP4293061A1 (en) | 2021-02-10 | 2022-02-04 | Polyester polyol, urethane prepolymer and polyurethane |
US18/264,529 US20240043602A1 (en) | 2021-02-10 | 2022-02-04 | Polyester polyol, urethane prepolymer and polyurethane |
JP2022580611A JPWO2022172879A1 (ja) | 2021-02-10 | 2022-02-04 | |
KR1020237026823A KR20230144021A (ko) | 2021-02-10 | 2022-02-04 | 폴리에스테르 폴리올, 우레탄 프레폴리머 및 폴리우레탄 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021020017 | 2021-02-10 | ||
JP2021-020017 | 2021-02-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022172879A1 true WO2022172879A1 (ja) | 2022-08-18 |
Family
ID=82837852
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/004518 WO2022172879A1 (ja) | 2021-02-10 | 2022-02-04 | ポリエステルポリオール、ウレタンプレポリマー及びポリウレタン |
Country Status (7)
Country | Link |
---|---|
US (1) | US20240043602A1 (ja) |
EP (1) | EP4293061A1 (ja) |
JP (1) | JPWO2022172879A1 (ja) |
KR (1) | KR20230144021A (ja) |
CN (1) | CN116917372A (ja) |
TW (1) | TW202241987A (ja) |
WO (1) | WO2022172879A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60190735A (ja) | 1983-12-13 | 1985-09-28 | サノフイ | 3−ヒドロキシ−3−メチルグルタル酸の製造方法 |
JPH07258148A (ja) | 1994-03-23 | 1995-10-09 | Kuraray Co Ltd | 3−メチルグルタル酸の製造方法 |
JPH0931388A (ja) * | 1995-07-21 | 1997-02-04 | Kuraray Co Ltd | 印刷インキ用のバインダーおよび該バインダーを含有する印刷インキ組成物 |
JPH0931173A (ja) * | 1995-07-21 | 1997-02-04 | Kuraray Co Ltd | ポリエステル系の可塑剤 |
JP2018502059A (ja) * | 2014-11-12 | 2018-01-25 | ビゾリス インコーポレイテッド | メバロノラクトンから調製されるポリマーおよび誘導体 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6026018A (ja) | 1983-07-21 | 1985-02-08 | Kuraray Co Ltd | 優れた耐加水分解性を有するポリウレタンの製造法 |
JPH082948B2 (ja) | 1987-01-22 | 1996-01-17 | 株式会社クラレ | ポリエステル |
-
2022
- 2022-02-04 CN CN202280013784.4A patent/CN116917372A/zh active Pending
- 2022-02-04 KR KR1020237026823A patent/KR20230144021A/ko unknown
- 2022-02-04 US US18/264,529 patent/US20240043602A1/en active Pending
- 2022-02-04 JP JP2022580611A patent/JPWO2022172879A1/ja active Pending
- 2022-02-04 WO PCT/JP2022/004518 patent/WO2022172879A1/ja active Application Filing
- 2022-02-04 EP EP22752703.3A patent/EP4293061A1/en active Pending
- 2022-02-09 TW TW111104705A patent/TW202241987A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60190735A (ja) | 1983-12-13 | 1985-09-28 | サノフイ | 3−ヒドロキシ−3−メチルグルタル酸の製造方法 |
JPH07258148A (ja) | 1994-03-23 | 1995-10-09 | Kuraray Co Ltd | 3−メチルグルタル酸の製造方法 |
JPH0931388A (ja) * | 1995-07-21 | 1997-02-04 | Kuraray Co Ltd | 印刷インキ用のバインダーおよび該バインダーを含有する印刷インキ組成物 |
JPH0931173A (ja) * | 1995-07-21 | 1997-02-04 | Kuraray Co Ltd | ポリエステル系の可塑剤 |
JP2018502059A (ja) * | 2014-11-12 | 2018-01-25 | ビゾリス インコーポレイテッド | メバロノラクトンから調製されるポリマーおよび誘導体 |
Also Published As
Publication number | Publication date |
---|---|
KR20230144021A (ko) | 2023-10-13 |
US20240043602A1 (en) | 2024-02-08 |
EP4293061A1 (en) | 2023-12-20 |
CN116917372A (zh) | 2023-10-20 |
JPWO2022172879A1 (ja) | 2022-08-18 |
TW202241987A (zh) | 2022-11-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6632866B2 (en) | Aliphatic thermoplastic polyurethanes and use thereof | |
EP3087118B1 (en) | A polyol based on dimer fatty acid residues and the corresponding polyurethanes | |
EP2888305B1 (en) | Polyurethanes | |
EP0299068B1 (en) | Process for producing polyurethane | |
KR20150113057A (ko) | 재생가능한 원재료를 포함하는 수분-경화성 폴리우레탄 조성물 | |
EP3105270B1 (en) | Polyurethane elastomers | |
TW201307416A (zh) | 具有降低起霧傾向之源自生物基質二醇之熱塑性聚胺甲酸酯 | |
JP2002293872A (ja) | 脂肪族熱可塑性ポリウレタンおよびそれらの使用 | |
CN112839976B (zh) | 包含生物基聚酯多元醇的热熔粘合剂组合物 | |
CA2346528C (en) | Mouldings of thermoplastic polyurethanes exhibiting reduced fogging | |
KR20220045957A (ko) | 열가소성 가공성 폴리우레탄 중합체를 제조하는 방법 | |
JP2020514428A (ja) | 高い引裂き伝播強度を有する熱可塑性ポリウレタン | |
JPH0354967B2 (ja) | ||
JP2008037987A (ja) | 水性ポリウレタン組成物 | |
WO2022172879A1 (ja) | ポリエステルポリオール、ウレタンプレポリマー及びポリウレタン | |
EP2279218B1 (en) | Thermoplastic polyurethanes with good fuel resistance | |
JPS63202610A (ja) | ポリウレタンの製造法 | |
US20170198087A1 (en) | Polyurethane | |
JP2011190392A (ja) | 発泡体 | |
CN112739737B (zh) | 具有改善的硬度的聚氨酯 | |
US20110172321A1 (en) | Hotmelt viscosity stabilizer | |
JP3324890B2 (ja) | ポリウレタンおよびそれに用いるポリエステルジオール | |
JPH11322885A (ja) | ポリウレタンの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22752703 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022580611 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280013784.4 Country of ref document: CN Ref document number: 18264529 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022752703 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022752703 Country of ref document: EP Effective date: 20230911 |