JPS6357452B2 - - Google Patents
Info
- Publication number
- JPS6357452B2 JPS6357452B2 JP6611678A JP6611678A JPS6357452B2 JP S6357452 B2 JPS6357452 B2 JP S6357452B2 JP 6611678 A JP6611678 A JP 6611678A JP 6611678 A JP6611678 A JP 6611678A JP S6357452 B2 JPS6357452 B2 JP S6357452B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- parts
- group
- polyester
- oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000728 polyester Polymers 0.000 claims description 51
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 239000004593 Epoxy Substances 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 10
- 238000006459 hydrosilylation reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- -1 diallyl ester Chemical group 0.000 description 8
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 8
- 239000005048 methyldichlorosilane Substances 0.000 description 8
- 238000006884 silylation reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical class COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 125000004423 acyloxy group Chemical group 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000001475 halogen functional group Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- AONDIGWFVXEZGD-UHFFFAOYSA-N diacetyloxy(methyl)silicon Chemical compound CC(=O)O[Si](C)OC(C)=O AONDIGWFVXEZGD-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler 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
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003973 paint Substances 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
- 239000000049 pigment Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 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 description 1
- 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 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- MZFBKHCHWCYNSO-UHFFFAOYSA-N [acetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[SiH](OC(C)=O)C1=CC=CC=C1 MZFBKHCHWCYNSO-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 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
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- XNAFLNBULDHNJS-UHFFFAOYSA-N dichloro(phenyl)silicon Chemical compound Cl[Si](Cl)C1=CC=CC=C1 XNAFLNBULDHNJS-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- MAWLKRJXJGHDRD-UHFFFAOYSA-N ethene;platinum Chemical group [Pt].C=C MAWLKRJXJGHDRD-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940049920 malate Drugs 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Description
この発明は、新規な常温硬化性ポリエステルオ
リゴマーの製造方法に関する。
本発明で製造されるオリゴマーは、
（式中、Ｒ，R1，R2は水素または炭素数１〜
10のアルキル基、アリール基、アラルキル基より
選ばれる１価の炭化水素基、R3は炭素数０〜10
の２価の炭化水素基、Ｘはハロゲン、アルコキ
シ、アシロキシ基より選ばれる基、ａは０〜２の
整数、ｂは０または１の整数である。）
で示されるシリル基を分子中に少なくとも１つ以
上有し、分子量が300〜10000の常温硬化性で主鎖
にエーテル結合を含まないポリエステルオリゴマ
ーである。
オリゴマーに種々の官能基を導入し、機能性を
付与し、そのままもしくは変性反応の中間体とし
て利用する試みが界面活性剤、塗料、接着剤、シ
ーラント、印刷インキ等の分野で行われている。
ポリエステル系オリゴマーに関してはシリコン
変性アルキドのように加水分解性基を有したシリ
コン基をケイ素―酸素結合を介してアルキド樹脂
に導入する事により、塗膜の密着性、塗膜強度、
耐油性、耐溶剤性を向上させる事がすでに知られ
ている。しかし本発明のように式(1)で示されるよ
うなシリル基を含するポリエステルオリゴマーは
知られていない。
本発明で製造されるポリエステルオリゴマー
は、そのままで液状であるか、もしくは少量の溶
媒の添加により容易に液状となり、大気中に暴露
すると常温で容易に硬化し得るオリゴマーを提供
する事、また各種金属プラスチツク、ガラスなど
の基材に対して密着性のすぐれた硬化性オリゴマ
ーを提供する事にある。
本発明により製造されるシリル基含有ポリエス
テルオリゴマーは、式
（式中、Ｒは炭素数１〜10までのアルキル基、
アリール基、アラルキル基より選ばれる１価の炭
化水素基、Ｘはハロゲン、アルコキシ、アシロキ
シ基より選ばれる基、ａは０〜２の整数）
で示されるヒドロシラン化合物を、主鎖がポリエ
ステル結合からなり分子末端又は側鎖に炭素―炭
素二重結合を有する分子量200〜8000のエーテル
結合を含まないポリエステルオリゴマーに白金錯
体の触媒の存在下で反応させることにより容易に
製造することが出来る。
本発明に使用する炭素―炭素二重結合を有する
ポリエステルオリゴマーは種々の方でつくる事が
出来る。
末端水酸基ポリエステル（商品名デスモフエ
ン、日本ポリウレタン社製）を水素化ナトリウ
ムのような塩基の存在下、アリルクロライドと
反応させる。
特開昭51―142027のように末端水酸基ポリエ
ステルとジアリルフタレートのようなジアリル
エステルをトルエンスルホン酸のようなエステ
ル交換触媒の存在下でエステル交換させる事に
よつて得る。
酸成分過剰の条件下で二塩基酸とジオールを
縮合させ、反応途中あるいは、反応後に炭素―
炭素二重結合を有するモノアルコールを加えて
エステル化する。
アクリロイル基含有のポリエステルを公知の
方法によりジオールと二塩基酸とアクリル酸
（またはメタクリル酸）の縮合により得る。
ポリエステル合成の際に、ジオール成分とし
て、炭素―炭素二重結合を有するエポキシ化合
物を一部を加えておくことにより、二塩基酸と
ジオールの縮合を行う。
特開昭54―91590のようにアルコール、エポ
キシ化合物、酸無水物を３級アミンの存在下に
反応させポリエステルを得る場合、アルコール
成分として炭素―炭素二重結合を有するモノア
ルコール、および（または）エポキシ成分とし
て炭素―炭素二重結合を有するエポキシ化合物
を一部、または全部用いる等の方法がある。
〜の方法におけるポリエステルの原料とし
て公知の二塩基酸、グリコール類、多価アルコー
ル類の使用が可能であり、以下例示すると、
〔２価アルコール〕
エチレングリコール、プロピレングリコール、
ブタンジオール、ヘキサメチレングリコール、水
素化ビスフエノールＡ、ネオペンチルグリコール
〔３価以上の多価アルコール〕
グリセリン、トリメチロールメタン、トリメチ
ロールプロパン、ペンタエリスリトール
〔２価カルボン酸〕
フタル酸、イソフタル酸、テレフタル酸、テト
ラヒドロフタル酸、ヘキサヒドロフタル酸、テト
ラクロルフタル酸、ポリブタジエンカルボン酸、
蓚酸、マロン酸、コハク酸、アジピン酸、セバシ
ン酸、マレイン酸、フマル酸、シクロペンタジカ
ルボン酸
〔３価以上の多価カルボン酸〕
トリメリツト酸、ブタントリカルボン酸、ピロ
メリツト酸
更に上記カルボン酸の無水物、アシルハライド
なども多価カルボン酸と同様に用いることができ
る。
炭素―炭素二重結合をポリエステルに導入する
為に用いられる化合物として具体的には次のもの
があげられる。前記との方法で用いるモノア
ルコールとしてはアリルアルコール、メタアリル
アルコール等；との方法で用いるエポキシ化
合物としてはアリルグリシジルエーテル、グリシ
ジルアクリレート、グリシジルメタクリレート等
がある。
〜の方法の中での合成法が、一分子中の
炭素―炭素二重結合の数を任意にコントロール出
来、また縮合副生成物を生じないなど最も適して
いる。の方法に用いられる原料を以下例示する
と次の通り。
〔アルコール〕
メタノール、エタノール、プロパノール、ブタ
ノール、アリルアルコール、メタアリルアルコー
ル等の１価のアルコール、前記の２価以上の多価
アルコール
〔エポキシ化合物〕
エチレンオキサイド、プロピレンオキサイド、
ブチレンオキサイド、エピクロルヒドリン、アリ
ルグリシジルエーテル、グリシジルアクリレー
ト、グリシジルメタクリレート、スチレンオキサ
イド、シクロヘキセンオキサイド、エピコート
828
（シエル化学社製〕
〔酸無水物〕
無水フタル酸、ジ，テトラ，またはヘキサヒド
ロ無水フタル酸、無水コハク酸、無水マレイン
酸、無水クロルマレイン酸、無水ピロメリツト
酸、無水ポリシジピン酸、無水ポリセバシン酸、
無水ポリイソフタル酸
等がある。又、反応の触媒としては３級アミン、
４級アンモニウム塩などが用いられ、反応温度が
比較的低温（70℃〜150℃）でも実施できる。
この合成法で、例えば酸無水物およびエポキ
シ化合物を１価のアルコールの存在下に反応させ
れば、次式のものが得られる。
（但しR5，R6及びR7は各々酸無水物、エポキ
シ化合物およびアルコールの残基であり通常炭素
数１〜30の有機基、ｎは１〜50の整数である）
アルコールとしてアリルアルコールを使用すれ
ばR7はCH2＝CH―CH2―で示される。エポキイ
化合物としてその１部、または全部アリルグリシ
ジルエーテルを用いるとR6は
グリシジルアクリレートである場合は
またグリシジルメタアクリレートである場合は
を含む形となる。
の方法では得られるポリエステルオリゴマー
の分子量をアルコールの量により200〜8000の範
囲で自由にコントロール出来、またオリゴマー中
の炭素―炭素二重結合の量も、用いる炭素―炭素
二重結合を有するアルコールおよび（または）エ
ポキシ化合物の量により変え得る。また上記の式
は１価のアルコールを使用したので、アルコール
酸基は末端にあるが、必ずしも分子末端に存在す
る必要はなく、多価アルコールを使用する場合は
ポリエステル間に挿入された形で存在する。
本発明のシリル基含有ポリエステルオリゴマー
の製造方法は、一般式
The present invention relates to a novel method for producing a room-temperature curable polyester oligomer. The oligomer produced by the present invention is (In the formula, R, R 1 and R 2 are hydrogen or have 1 to 1 carbon atoms.
A monovalent hydrocarbon group selected from 10 alkyl groups, aryl groups, and aralkyl groups, R 3 has 0 to 10 carbon atoms
is a divalent hydrocarbon group, X is a group selected from halogen, alkoxy, and acyloxy groups, a is an integer of 0 to 2, and b is an integer of 0 or 1. ) It is a polyester oligomer that has at least one silyl group shown in the formula in its molecule, has a molecular weight of 300 to 10,000, is curable at room temperature, and does not contain an ether bond in its main chain. Attempts have been made in the fields of surfactants, paints, adhesives, sealants, printing inks, etc. to introduce various functional groups into oligomers to impart functionality and use them as they are or as intermediates for modification reactions. Regarding polyester oligomers, by introducing a silicon group with a hydrolyzable group into the alkyd resin through a silicon-oxygen bond, as in silicon-modified alkyd, the adhesion of the coating film, the strength of the coating film,
It is already known to improve oil resistance and solvent resistance. However, a polyester oligomer containing a silyl group as represented by formula (1) as in the present invention is not known. The polyester oligomer produced by the present invention is liquid as it is, or easily becomes liquid by adding a small amount of solvent, and can be easily cured at room temperature when exposed to the atmosphere. The purpose is to provide a curable oligomer with excellent adhesion to base materials such as plastic and glass. The silyl group-containing polyester oligomer produced by the present invention has the formula (In the formula, R is an alkyl group having 1 to 10 carbon atoms,
A monovalent hydrocarbon group selected from aryl group and aralkyl group, X is a group selected from halogen, alkoxy, and acyloxy group, and a is an integer of 0 to 2). It can be easily produced by reacting a polyester oligomer, which does not contain an ether bond and has a molecular weight of 200 to 8,000 and has a carbon-carbon double bond at the molecular end or side chain, in the presence of a platinum complex catalyst. The polyester oligomer having a carbon-carbon double bond used in the present invention can be produced by various methods. A polyester with a terminal hydroxyl group (trade name Desmofene, manufactured by Nippon Polyurethane Co., Ltd.) is reacted with allyl chloride in the presence of a base such as sodium hydride. It is obtained by transesterifying a polyester with a terminal hydroxyl group and a diallyl ester such as diallyl phthalate in the presence of a transesterification catalyst such as toluenesulfonic acid, as disclosed in JP-A-51-142027. A dibasic acid and a diol are condensed under conditions with an excess of acid components, and carbon-
Esterification is carried out by adding a monoalcohol having a carbon double bond. An acryloyl group-containing polyester is obtained by condensation of a diol, a dibasic acid, and acrylic acid (or methacrylic acid) by a known method. During polyester synthesis, by adding a portion of an epoxy compound having a carbon-carbon double bond as a diol component, the dibasic acid and diol are condensed. When a polyester is obtained by reacting an alcohol, an epoxy compound, and an acid anhydride in the presence of a tertiary amine as in JP-A-54-91590, the alcohol component is a monoalcohol having a carbon-carbon double bond, and/or There are methods such as using part or all of an epoxy compound having a carbon-carbon double bond as the epoxy component. Known dibasic acids, glycols, and polyhydric alcohols can be used as raw materials for polyester in the method of ~.
Butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol [trivalent or higher polyhydric alcohol] Glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol [divalent carboxylic acid] Phthalic acid, isophthalic acid, terephthalic acid acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, polybutadienecarboxylic acid,
Oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, cyclopentadicarboxylic acid [trivalent or higher polyhydric carboxylic acid] trimellitic acid, butanetricarboxylic acid, pyromellitic acid, and anhydrides of the above carboxylic acids , acyl halides, etc. can also be used in the same way as polyhydric carboxylic acids. Specific examples of compounds used to introduce carbon-carbon double bonds into polyester include the following. The monoalcohols used in the above method include allyl alcohol, methalyl alcohol, etc.; the epoxy compounds used in the above method include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, etc. Among the methods listed in ~, the synthesis method is the most suitable as it allows the number of carbon-carbon double bonds in one molecule to be controlled arbitrarily and does not produce condensation by-products. Examples of raw materials used in the method are as follows. [Alcohol] Monohydric alcohols such as methanol, ethanol, propanol, butanol, allyl alcohol, methalyl alcohol, the above-mentioned polyhydric alcohols of dihydric or higher hydricity [Epoxy compounds] Ethylene oxide, propylene oxide,
Butylene oxide, epichlorohydrin, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, styrene oxide, cyclohexene oxide, Epicote
828 (manufactured by Ciel Chemical Co., Ltd.) [Acid anhydride] Phthalic anhydride, di-, tetra-, or hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, chlormaleic anhydride, pyromellitic anhydride, polysidipic anhydride, polysebacic anhydride ,
Examples include polyisophthalic anhydride. In addition, as a reaction catalyst, tertiary amine,
Quaternary ammonium salts and the like are used, and the reaction can be carried out at relatively low temperatures (70°C to 150°C). By this synthesis method, for example, if an acid anhydride and an epoxy compound are reacted in the presence of a monohydric alcohol, the following formula can be obtained. (However, R 5 , R 6 and R 7 are residues of an acid anhydride, an epoxy compound, and an alcohol, respectively, and are usually organic groups having 1 to 30 carbon atoms, and n is an integer of 1 to 50.) Allyl alcohol is used as the alcohol. If used, R 7 is represented by CH 2 =CH-CH 2 -. When a part or all of allyl glycidyl ether is used as the epoxy compound, R 6 is If glycidyl acrylate Also, if it is glycidyl methacrylate, It is a form that includes. In this method, the molecular weight of the polyester oligomer obtained can be freely controlled within the range of 200 to 8,000 by the amount of alcohol, and the amount of carbon-carbon double bonds in the oligomer can also be controlled depending on the alcohol having carbon-carbon double bonds and the amount of carbon-carbon double bonds in the oligomer. (or) may vary depending on the amount of epoxy compound. Also, since the above formula uses a monohydric alcohol, the alcoholic acid group is at the end, but it does not necessarily have to be at the end of the molecule, and when a polyhydric alcohol is used, it exists in the form inserted between polyesters. do. The method for producing the silyl group-containing polyester oligomer of the present invention has the general formula
【式】（Ｒ，
Ｘ，ａは前述の通り）で示されるヒドロシラン化
合物を、主鎖がポリエステル結合からなり分子末
端又は側鎖に炭素―炭素二重結合を有し主鎖にエ
ーテル結合を含まない分子量200〜8000のポリエ
ステルオリゴマーと白金錯体の触媒存在下で反応
させることにより容易に製造される。
上記一般式に含まれるヒドラシラン化合物を具
体的に例示するとトリクロルシラン、メチルジク
ロシラン、ジメチルクロルシラン、フエニルジク
ロルシランの如きハロゲン化ラン類；トリメトキ
シシラン、トリエトキシシラン、メチルジエトキ
シシラン、メチルジメトキシシラン、フエニルジ
メトキシシランの如きアルコキシシラン類；トリ
アセトキシシラン、メチルジアセトキシシランお
よびフエニルジアセトキシシランの如きアシロキ
シシラン類等の各種シラン類が挙げられる。
用いるヒドロシラン化合物の量は、ポリエステ
ルオリゴマーに含まれる炭素―炭素二重結合に対
し任意量の使用が可能であるが、0.5〜２倍モル
の使用が好ましい。これ以上のシラン量の使用を
妨げるものではないが、未反応のヒドロシランと
して回収されるだけである。
更に、本発明ではヒドロシラン化合物として安
価な基礎原料で高反応性のハロゲン化シラン類が
容易に使用できる。ハロゲン化シランを用いて得
られるシリル基含有ポリエステルオリゴマーは空
気中に暴露すると塩化水素を発生しながら常温に
て速やかに硬化するが、塩化水素による刺激臭や
腐蝕に問題があり、限定された用途にしか実用上
使用できないので、更に続いてハロゲン官能基を
他の加水分解性官能基に変換することが望まし
い。加水分解性基としてはアルコキシ基、アシロ
キシ基が挙げられる。
ハロゲン官能基を、これら加水分解性官能基に
変換する方法としては、メタノール、エタノー
ル、２―メトキシエタノール、sec―ブタノール、
tert―ブタノールの如きアルコール類、アルコ
ール類のアルカリ金属塩、オルトギ酸メチル、
オルトギ酸エチルの如きアルトギ酸アルキル類、
などをハロゲン官能基と反応させる方法が具体的
に挙げられる。
アシロキシ基に変換する方法としては、酢
酸、プロピオン酸、安息香酸の如きカルボン酸
類、カルボン酸類のアルカリ金属塩、などをハ
ロゲン官能基と反応させる方法が具体的に挙げら
れる。
本発明においては、ヒドロシラン化合物を炭素
―炭素二重結合に反応させる段階で、白金錯体の
触媒を必要とする。このヒドロシリル化反応は50
〜150℃の任意の温度にて達成され、反応時間は
１〜４時間程度で充分である。
ヒドロシリル化反応によりポリエステルオリゴ
マーに導入されるシリル基に関しハロゲン官能基
の場合のみ他の加水分解性官能基に変換するので
はなく、他のアルコキシ基やアシロキシ基などの
場合も必要に応じて他の加水分解性官能基に変換
することができる。このようにヒドロシリル化反
応により直接導入されるシリル基上の加水分解性
基を他の加水分解性基に変換する温度は20〜120
が適当である。又、これらの変換反応は溶剤を使
用してもしなくても達成されうるが、使用する場
合はエーテル類及び炭化水素類の如き不活性な溶
剤が適当である。
本発明においてヒドロシリル化反応に供される
〜の方法で合成された炭素―炭素二重結合を
有するポリエステルの中に水酸基を含有している
ものがある。この場合ヒドロシリル化反応におい
てハロゲン化シラン類が用いられる場合には、ヒ
ドロキシル基とハロゲン化シラン類のハロゲンと
が反応を起し、ポリエステルがアルコキシ結合に
て珪素原子と結合することにより、反応途中でゲ
ル化を起こしてしまう場合がある。それ故ヒドロ
シリル化反応に先立つて無水酢酸やA hydrosilane compound represented by the formula (R, It is easily produced by reacting a polyester oligomer with a molecular weight of 200 to 8,000 in the presence of a platinum complex catalyst. Specific examples of hydrasilane compounds included in the above general formula include halogenated ranes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane; Examples include various silanes such as alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; and acyloxysilanes such as triacetoxysilane, methyldiacetoxysilane and phenyldiacetoxysilane. The amount of the hydrosilane compound to be used can be any amount with respect to the carbon-carbon double bond contained in the polyester oligomer, but it is preferably used in an amount of 0.5 to 2 times the mole. Although this does not preclude the use of larger amounts of silane, it will simply be recovered as unreacted hydrosilane. Furthermore, in the present invention, halogenated silanes, which are inexpensive basic raw materials and have high reactivity, can be easily used as the hydrosilane compound. When exposed to air, silyl group-containing polyester oligomers obtained using halogenated silanes harden rapidly at room temperature while generating hydrogen chloride. However, they have problems with the irritating odor and corrosion caused by hydrogen chloride, so their use is limited. It is desirable to subsequently convert the halogen functional group to another hydrolyzable functional group, since it can only be used in practice. Examples of the hydrolyzable group include an alkoxy group and an acyloxy group. Methods for converting halogen functional groups into these hydrolyzable functional groups include methanol, ethanol, 2-methoxyethanol, sec-butanol,
Alcohols such as tert-butanol, alkali metal salts of alcohols, methyl orthoformate,
Alkyl althoformates such as ethyl orthoformate,
A specific example is a method of reacting the like with a halogen functional group. Specific examples of the method for converting into an acyloxy group include a method in which carboxylic acids such as acetic acid, propionic acid, and benzoic acid, alkali metal salts of carboxylic acids, and the like are reacted with a halogen functional group. In the present invention, a platinum complex catalyst is required in the step of reacting a hydrosilane compound with a carbon-carbon double bond. This hydrosilylation reaction is 50
This can be achieved at any temperature between ~150°C, and a reaction time of about 1 to 4 hours is sufficient. Regarding the silyl groups introduced into polyester oligomers through the hydrosilylation reaction, we do not convert only halogen functional groups into other hydrolyzable functional groups, but also convert other alkoxy groups, acyloxy groups, etc. into other groups as necessary. It can be converted into a hydrolyzable functional group. The temperature at which the hydrolyzable group on the silyl group directly introduced by the hydrosilylation reaction is converted into another hydrolyzable group is 20 to 120°C.
is appropriate. These conversion reactions can also be accomplished with or without the use of solvents; however, when used, inert solvents such as ethers and hydrocarbons are suitable. Some of the polyesters having a carbon-carbon double bond synthesized by the method of ~ to which are subjected to the hydrosilylation reaction in the present invention contain hydroxyl groups. In this case, when halogenated silanes are used in the hydrosilylation reaction, the hydroxyl group and the halogen of the halogenated silanes react, and the polyester is bonded to the silicon atom through an alkoxy bond. It may cause gelation. Therefore, prior to the hydrosilylation reaction, acetic anhydride and
【式】結
合を有しないハロゲン化シラン、例えばトリメチ
ルクロルシラン等で前処理し、重合体中にヒドロ
キシル基が残存しない状態となし、未反応のハロ
ゲン化シラン類や無水酢酸類及び生成する塩酸や
酢酸を取り除いた後、ヒドロシリル化反応を行う
という手順を踏む事が好ましい。
の方法で合成された炭素―炭素二重結合を含
むポリエステルをヒドロシリル化すると下記の構
造のシリル基
（Ｒ，R1，R2，R3，Ｘ，ａ，ｂは前述の通り、
R4は炭素数１〜10のアルキル基）
が導入され、具体的には、ポリエステルのエポキ
シ成分としてアリルグリシジルエーテルを用いる
と
また、グリシジルアクリレートを用いると
また、グリシジルメタクリレートを用いると
となる。
シリル基含有ポリエステルオリゴマーは前記の
方法以外でも製造する事が出来る。例えばアルコ
ール、エポキシ化合物、酸無水物を３級アミン存
在下で反応させる際にエポキシ成分として、例え
ばγ―グリシロキシプロピルトリメトキシシラン
を用いて反応させる事により可能である。
本発明により製造されるシリル基含有の新規ポ
リエステルオリゴマーは、大気中に暴露されると
常温で網状組織を形成し硬化する。この場合の硬
化速度は大気温度、相対湿度および加水分解性基
の種類により変化するので使用にあたつては特に
加水分解性基の種類を充分考慮する必要がある。
本発明により製造されるシリル基含有ポリエス
テルオリゴマーを硬化させるにあたつては硬化促
進剤を使用してもしなくてもよい。硬化促進剤を
使用する場合にはアルキルチタン酸塩、オクチル
酸錫、ジブチル錫ラウレート等の如きカルボン酸
の金属塩、ジブチルアミン―２―ヘキソエート等
の如きアミン塩ならびに他の酸性触媒および塩基
性触媒が有効である。これら硬化促進剤の添加量
は該オリゴマーに対し0.001〜10重量％で使用す
るのが好ましい。
本発明で製造されるシリル基含有ポリエステル
オリゴマーは、表面光沢にすぐれ、また金属、ガ
ラスに密着性の良好な塗膜を与え、建造物、航空
機、自動車、電子材料等の被覆組成物、密封組成
物、塗料組成物として使用可能である。また、食
品包装材料、注型材料、型取り用材料、各種無機
物の表面処理剤としても有用である。
このような硬化組成物の原料として１分子中の
加水分解性シリル基の数は１個でもよいが、２個
以上のものが表面硬度、耐熱性、耐沸水性、耐溶
剤性等の物性上好ましく、またシリル基当量（シ
リル基１個あたりの分子量）が200〜750、特に
200〜550のものが好ましい。
また本硬化物の特徴はエチルシリケート系、ま
たはKR212、213等（信越化学社製）のシリコン
系の共縮合モノマーの添加により塗膜の表面硬
度、塗膜強度、耐溶剤性をコントロールできる事
にもある。また該オリゴマーは種々の充填剤、顔
料等を混入することが可能である。充填剤、顔料
としては各種シリカ類、炭酸カリシウム、炭酸マ
グネシウム、酸化チタン、酸化鉄、ガラス繊維等
が挙げられる。
このような加水分解性シリル基を分子中に少な
くとも１つ以上有するポリエステルオリゴマーは
新規なものであり、その構造は製法および実施例
中の検定により明らかである。
以下具体的な実施例を挙げて説明するが、本発
明はこれらの実施例だけに限定されるものではな
い、以下に示す部数は特にことわらない限り、重
量部をあらわす。
実施例 １
市販の分子量500の両末端にアクリロイル基を
有する液状ポリエステル（東亜合成化学社製、商
品名アロニクスM6100）100部を窒素置換された
フラスコに入れる。窒素気流下メチルジクロルシ
ラン55.2部および白金エチレン錯体0.01部を加え
100℃、３時間撹拌下に反応させる。反応終了後
未反応のメチルジシクロルシランを減圧下で除い
た。更に60℃で撹拌下でオルトギ酸メチル85部加
え、生成する塩化メチルを除きながら約30分反応
させると系は中性になつた。減圧下、揮発分（塩
化メチル、ギ酸メチル、オルトギ酸メチル）を除
き、淡黄色の液体を得た。その赤外吸収スペクト
ルには1630，1615cm-1のアクリロイル基の吸収は
完全に消失していた。ジプチル錫マレート２部を
加えて錫板上に塗布すると約３時間でタツクフリ
ーとなり、７日後鉛筆硬度HBの塗膜が得られ
た。
参考例 １
148部（１モル）の無水フタル酸、34.8部（0.6
モル）のプロピレンオキサイド（PO）45.6部
（0.4モル）のアリルグリシジルエーテル11.6部
（0.2モル）のアリルアルコール、0.5部のジメチ
ルベンジルアミンを１金属製オートクレーブい
仕込み、100℃撹拌下で反応させた。３時間後に
4.6部のPOを加えて更に１時間反応させ酸価が0.5
に達した後、過剰のPOを除き無色粘稠なオリゴ
マーを得た。得られたオリゴマーの分子量は1200
であつた。
更に、得られたポリエステルオリゴマー100部
に対し、10.2部（0.1モル）の無水酢酸を加え、
120℃で２時間反応させた後、無水酢酸を減圧下
で除去した。得られたオリゴマーの分子量1250、
オレフイン当量429、末端水酸基のアセチル化率
は70％であつた。
実施例 ２
参考例１で合成したアセチル化したポリエステ
ルオリゴマー100部、塩化白金酸（イソプロパノ
ール：テトラヒドロフランの体積比１：10の混合
溶媒で重量比約20倍に稀釈したもの）0.012部メ
チルジクロルシラン32.2部加え、80℃で４時間撹
拌下で反応させる。反応終了後、未反応のメチル
ジクロルシランを減圧下で除去する。これにメタ
ノール30部加え１時間室温下で撹拌し、減圧下で
生成する塩化水素ガス、過剰のメタノールを除去
する。更に少量のプロピレンオキサイドを加えて
この系を中性にする。最終に減圧下で揮発成分を
除き、淡黄色の粘稠なオリゴマーを得た。図に
その赤外吸収スペクトルを示した。1645cm-1のオ
レフインの吸収は完全に消失しており、シリル化
率（ヨウ素滴定により求めた）は98％であつた。
得られた生成物にジブチル錫ラウレート２部を加
え、ガラス板上に塗布した所、１時間でタツクフ
リーとなり、３日後の鉛筆硬度は2Hであつた。
実施例 ３
同様に参考例１のアセチル化したポリエステル
オリゴマー100部に塩化白金酸0.012部、メチルジ
メトキシシラン29.6部加え、80℃で３時間撹拌下
で反応させる。反応終了後、未反応のメチルジメ
トキシシランを減圧下で除去する。得られたポリ
エステルのシリル化率は90％であつた。得られた
生成物にジブチル錫ラウレート２部加え、ガラス
板上に塗布した所、１時間でタツクフリーとな
り、３日後の鉛筆硬度は2Hであつた。
参考例 ２〜５
無水フタル酸、ブチレンオキサイド、アリルグ
リシジルエーテル、アリルアルコールを用い、参
考例１と同様の方法により反応させ、表のよう
な分子量、オレフイン当量を持つ末端アリル基含
有ポリエステルオリゴマーのアセチル化物を得
た。
実施例 ４〜７
参考例２〜５で得られたアセチル化ポリエステ
ルオリゴマーに対し、何れも実施例３の方法によ
りメチルジメトキシシランを炭素―炭素二重結合
に対し1.2倍モル、塩化白金酸を１×10-4倍モル
加え80℃、４時間反応させた。得られたシリル基
含有ポリエステルのシリル化率および塗膜物性を
表にまとめた。
実施例 ８
参考例４で得られた末端アリル基含有ポリエス
テルオリゴマーのアセチル化物100部に対し塩化
白金酸0.009部、トリクロルシラン28部加え、80
℃で４時間撹拌下で反応させた。反応終了後、未
反応のトリクロルシランを減圧下で除去後、これ
にメタノール33部を加え１時間室温で撹拌し、減
圧下で生成する塩化水素ガス、過剰のメタノール
を除去し、プロピレンオキサイドを少量加えて、
この糸を中性にした。最後に減圧下で揮発成分を
除き、淡黄色の粘稠なオリゴマーを得た。得られ
たシリル基含有ポリエステルのシリル化率および
塗膜物性を表に示した。シリル化反応は用いた
条件下でほぼ定量的に進行する。本シリル基含有
ポリエステルは密着性衝撃性に非常にすぐれる事
がわかる。[Formula] Pre-treat with a halogenated silane that does not have a bond, such as trimethylchlorosilane, so that no hydroxyl groups remain in the polymer, and remove unreacted halogenated silanes, acetic anhydride, and generated hydrochloric acid. It is preferable to carry out a hydrosilylation reaction after removing acetic acid. Hydrosilylation of a polyester containing a carbon-carbon double bond synthesized by the method described above results in a silyl group with the following structure. (R, R 1 , R 2 , R 3 , X, a, b are as mentioned above,
R4 is an alkyl group having 1 to 10 carbon atoms) is introduced, and specifically, when allyl glycidyl ether is used as the epoxy component of polyester, Also, when glycidyl acrylate is used, Also, when using glycidyl methacrylate becomes. Silyl group-containing polyester oligomers can be produced by methods other than those described above. For example, this can be achieved by using, for example, γ-glysiloxypropyltrimethoxysilane as the epoxy component when reacting alcohol, epoxy compound, and acid anhydride in the presence of a tertiary amine. The novel silyl group-containing polyester oligomer produced by the present invention forms a network structure and hardens at room temperature when exposed to the atmosphere. In this case, the curing rate varies depending on atmospheric temperature, relative humidity, and the type of hydrolyzable group, so the type of hydrolyzable group must be carefully considered when using the resin. When curing the silyl group-containing polyester oligomer produced by the present invention, a curing accelerator may or may not be used. When curing accelerators are used, metal salts of carboxylic acids such as alkyl titanates, tin octylate, dibutyltin laurate, etc., amine salts such as dibutylamine-2-hexoate, etc., and other acidic and basic catalysts. is valid. The amount of these curing accelerators added is preferably 0.001 to 10% by weight based on the oligomer. The silyl group-containing polyester oligomer produced by the present invention has excellent surface gloss and provides coating films with good adhesion to metals and glass, and can be used as coating compositions and sealing compositions for buildings, aircraft, automobiles, electronic materials, etc. It can be used as a paint composition. It is also useful as a food packaging material, a casting material, a molding material, and a surface treatment agent for various inorganic materials. As a raw material for such a cured composition, the number of hydrolyzable silyl groups in one molecule may be one, but it is preferable to have two or more hydrolyzable silyl groups for physical properties such as surface hardness, heat resistance, boiling water resistance, and solvent resistance. Preferably, the silyl group equivalent (molecular weight per silyl group) is 200 to 750, especially
200-550 is preferred. In addition, a feature of this cured product is that the surface hardness, film strength, and solvent resistance of the coating film can be controlled by adding ethyl silicate-based or silicon-based co-condensation monomers such as KR212 and 213 (manufactured by Shin-Etsu Chemical Co., Ltd.). There is also. Moreover, various fillers, pigments, etc. can be mixed into the oligomer. Examples of fillers and pigments include various silicas, potassium carbonate, magnesium carbonate, titanium oxide, iron oxide, glass fiber, and the like. Such a polyester oligomer having at least one hydrolyzable silyl group in its molecule is new, and its structure is clear from the manufacturing method and assays in the Examples. The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples. Unless otherwise specified, the numbers shown below represent parts by weight. Example 1 100 parts of a commercially available liquid polyester having a molecular weight of 500 and having acryloyl groups at both ends (manufactured by Toagosei Kagaku Co., Ltd., trade name: Aronix M6100) is placed in a nitrogen-substituted flask. Add 55.2 parts of methyldichlorosilane and 0.01 part of platinum ethylene complex under a nitrogen stream.
React at 100°C for 3 hours with stirring. After the reaction was completed, unreacted methyldicyclosilane was removed under reduced pressure. Furthermore, 85 parts of methyl orthoformate was added under stirring at 60°C, and the reaction was allowed to proceed for about 30 minutes while removing the generated methyl chloride, and the system became neutral. Volatile components (methyl chloride, methyl formate, methyl orthoformate) were removed under reduced pressure to obtain a pale yellow liquid. In the infrared absorption spectrum, the absorption of acryloyl groups at 1630 and 1615 cm -1 completely disappeared. When 2 parts of diptyltin malate was added and applied on a tin plate, it became tack-free in about 3 hours, and a coating film with pencil hardness HB was obtained after 7 days. Reference example 1 148 parts (1 mol) of phthalic anhydride, 34.8 parts (0.6
45.6 parts (0.4 moles) of propylene oxide (PO), allyl glycidyl ether, 11.6 parts (0.2 moles) of allyl alcohol, and 0.5 parts of dimethylbenzylamine were placed in a metal autoclave and reacted under stirring at 100°C. . 3 hours later
Add 4.6 parts of PO and react for another hour until the acid value reaches 0.5.
After reaching the desired temperature, excess PO was removed to obtain a colorless viscous oligomer. The molecular weight of the obtained oligomer is 1200
It was hot. Furthermore, 10.2 parts (0.1 mol) of acetic anhydride was added to 100 parts of the obtained polyester oligomer,
After reacting at 120°C for 2 hours, acetic anhydride was removed under reduced pressure. The molecular weight of the obtained oligomer was 1250,
The olefin equivalent was 429, and the acetylation rate of the terminal hydroxyl group was 70%. Example 2 100 parts of the acetylated polyester oligomer synthesized in Reference Example 1, 0.012 parts of chloroplatinic acid (diluted to about 20 times the weight ratio with a mixed solvent of isopropanol:tetrahydrofuran at a volume ratio of 1:10), and 0.012 parts of methyldichlorosilane. Add 32.2 parts and react at 80°C for 4 hours with stirring. After the reaction is completed, unreacted methyldichlorosilane is removed under reduced pressure. Add 30 parts of methanol to this and stir at room temperature for 1 hour, and remove the hydrogen chloride gas and excess methanol produced under reduced pressure. A further small amount of propylene oxide is added to neutralize the system. Finally, volatile components were removed under reduced pressure to obtain a pale yellow viscous oligomer. The figure shows its infrared absorption spectrum. The absorption of olefin at 1645 cm -1 completely disappeared, and the silylation rate (determined by iodometric titration) was 98%.
When 2 parts of dibutyltin laurate was added to the obtained product and applied on a glass plate, it became tack-free in 1 hour, and the pencil hardness after 3 days was 2H. Example 3 Similarly, 0.012 parts of chloroplatinic acid and 29.6 parts of methyldimethoxysilane were added to 100 parts of the acetylated polyester oligomer of Reference Example 1, and the mixture was reacted at 80° C. for 3 hours with stirring. After the reaction is completed, unreacted methyldimethoxysilane is removed under reduced pressure. The silylation rate of the obtained polyester was 90%. When 2 parts of dibutyltin laurate was added to the obtained product and applied on a glass plate, it became tack-free in 1 hour, and the pencil hardness was 2H after 3 days. Reference Examples 2 to 5 Phthalic anhydride, butylene oxide, allyl glycidyl ether, and allyl alcohol were reacted in the same manner as in Reference Example 1 to obtain acetyl terminal allyl group-containing polyester oligomers having the molecular weight and olefin equivalent as shown in the table. I got a monster. Examples 4 to 7 For the acetylated polyester oligomers obtained in Reference Examples 2 to 5, methyldimethoxysilane was added to the carbon-carbon double bond by 1.2 times the mole and chloroplatinic acid was added to the acetylated polyester oligomer by the method of Example 3. ×10 -4 times the mole was added and reacted at 80°C for 4 hours. The silylation rate and physical properties of the coating film of the obtained silyl group-containing polyester are summarized in the table. Example 8 0.009 parts of chloroplatinic acid and 28 parts of trichlorosilane were added to 100 parts of the acetylated product of the terminal allyl group-containing polyester oligomer obtained in Reference Example 4.
The reaction was carried out under stirring at ℃ for 4 hours. After the reaction is complete, unreacted trichlorosilane is removed under reduced pressure, 33 parts of methanol is added thereto, stirred at room temperature for 1 hour, hydrogen chloride gas generated under reduced pressure and excess methanol are removed, and a small amount of propylene oxide is added. In addition,
This thread was made neutral. Finally, volatile components were removed under reduced pressure to obtain a pale yellow viscous oligomer. The silylation rate and physical properties of the coating film of the obtained silyl group-containing polyester are shown in the table. The silylation reaction proceeds almost quantitatively under the conditions used. It can be seen that this silyl group-containing polyester has excellent adhesion and impact resistance.
【表】
実施例 ９
参考例１で合成したポリエステル100部、塩化
白金酸（イソプロパノール：テトラヒドロフラン
は１：10）0.012部、メチルジクロルシラン32.2
部加え、80℃で24時間撹拌下で反応させた。反応
終了後、未反応のメチルジクロルシランを減圧下
で除去し、これにフエノール63.2部加え５時間室
温下で撹拌し、減圧下で生成する塩化水素ガス過
剰のフエノールを除去した。更に少量のプロピレ
ンオキサイドを加えてこの系を中性にした。最後
に減圧下で揮発成分を除き、淡黄色の粘稠なオリ
ゴマーを得た。シリル化率（ヨウ素滴定法により
求めた）は98％であつた。得られた生成物にジブ
チル錫ラウレート２部を加え、ガラス板上に塗布
した所８時間でタツクフリーとなり、３日後の鉛
筆硬度はHBであつた。
実施例 10
参考例１で合成したポリエステル100部、塩化
白金酸（イソプロパノール：テトラヒドロフラン
は１：10）0.012部、メチルジクロルシラン32.2
部加え、80℃で４時間撹拌下で反応させた。反応
終了後、未反応のメチルジクロルシランを減圧下
で除去した。これにエチルメルカプタン41.7部を
加え５時間室温下で撹拌し、減圧下で生成する塩
化水素ガス、過剰のエチルメルカプタンを除去し
た。更に少量のプロピレンオキサイドを加え、こ
の系を中性にした。最後に、減圧下で揮発成分を
除き、淡黄白の粘稠なオリゴマーを得た。シリル
化率（ヨウ素滴定法により求めた）は98％であつ
た。得られた生成物にジブチル錫ラウレート２部
を加え、ガラス板上に塗布した所４時間でタツク
フリーとなり、３日後の鉛筆硬度はＨであつた。
実施例 11
参考例４で得られた末端アリル基含有ポリエス
テルオリゴマーのアセチル化物100部に対し、塩
化白金酸0.009部、メチルジアセトキシシラン
33.5部加え、80℃で４時間撹拌下で反応させた。
反応終了後、未反応のメチルジアセトキシシラン
を減圧下で除去した。得られたメチルジアセトキ
シシリル基含有ポリエステルのシリル化率は93％
であつた。
実施例４〜８と同様の方法で評価した塗膜物性
は、鉛筆硬度2H、エリクセン９mm以上、デユポ
ン衝撃性（3/8インチ撃芯）500ｇ・50cm合格であ
つた。[Table] Example 9 100 parts of the polyester synthesized in Reference Example 1, 0.012 parts of chloroplatinic acid (isopropanol:tetrahydrofuran: 1:10), 32.2 parts of methyldichlorosilane
of the mixture was added, and the mixture was reacted at 80°C for 24 hours with stirring. After the reaction was completed, unreacted methyldichlorosilane was removed under reduced pressure, 63.2 parts of phenol was added thereto, and the mixture was stirred at room temperature for 5 hours to remove excess phenol of hydrogen chloride gas produced under reduced pressure. A further small amount of propylene oxide was added to neutralize the system. Finally, volatile components were removed under reduced pressure to obtain a pale yellow viscous oligomer. The silylation rate (determined by iodometric titration) was 98%. 2 parts of dibutyltin laurate was added to the obtained product, and when it was applied on a glass plate, it became tack-free in 8 hours, and the pencil hardness after 3 days was HB. Example 10 100 parts of the polyester synthesized in Reference Example 1, 0.012 parts of chloroplatinic acid (isopropanol:tetrahydrofuran: 1:10), 32.2 parts of methyldichlorosilane
of the mixture was added, and the mixture was reacted at 80° C. for 4 hours with stirring. After the reaction was completed, unreacted methyldichlorosilane was removed under reduced pressure. 41.7 parts of ethyl mercaptan was added to the mixture and stirred at room temperature for 5 hours, and hydrogen chloride gas generated and excess ethyl mercaptan were removed under reduced pressure. A further small amount of propylene oxide was added to neutralize the system. Finally, volatile components were removed under reduced pressure to obtain a pale yellowish white viscous oligomer. The silylation rate (determined by iodometric titration) was 98%. 2 parts of dibutyltin laurate was added to the obtained product, and when it was coated on a glass plate, it became tack-free in 4 hours, and the pencil hardness was H after 3 days. Example 11 0.009 parts of chloroplatinic acid and methyldiacetoxysilane were added to 100 parts of the acetylated product of the terminal allyl group-containing polyester oligomer obtained in Reference Example 4.
33.5 parts were added and reacted at 80°C for 4 hours with stirring.
After the reaction was completed, unreacted methyldiacetoxysilane was removed under reduced pressure. The silylation rate of the obtained methyldiacetoxysilyl group-containing polyester was 93%.
It was hot. The physical properties of the coating film evaluated in the same manner as in Examples 4 to 8 were as follows: pencil hardness of 2H, Erichsen of 9 mm or more, and Dupont impact resistance (3/8 inch percussion core) of 500 g and 50 cm.
図は、本発明の実施例２で合成されたオリゴマ
ーの赤外線吸収スペクトルである。図中、下の吸
収スペクトルがヒドロシリル化前のアリル基含有
ポリエステルオリゴマーのもので、上の吸収スペ
クトルがヒドロシリル化後のものである。
The figure shows an infrared absorption spectrum of the oligomer synthesized in Example 2 of the present invention. In the figure, the lower absorption spectrum is that of the allyl group-containing polyester oligomer before hydrosilylation, and the upper absorption spectrum is that after hydrosilylation.
Claims (1)
あるいは側鎖に炭素―炭素二重結合を含有し、主
鎖にエーテル結合を含まない分子量200〜8000の
ポリエステルオリゴマーと、式 （式中、Ｒは炭素数１〜10までのアルキル基、
アリール基、アラルキル基より選ばれる１価の炭
化水素基、Ｘはハロゲン、アルコキシ、アシロキ
シ基より選ばれる基、ａは０〜２の整数） で示されるヒドロキシラン化合物を白金錯体触媒
の存在下、50〜150℃の温度で反応させることを
特徴とする新規な常温硬化性ポリエステルオリゴ
マーの製造方法。[Claims] 1. A polyester oligomer with a molecular weight of 200 to 8,000 whose main chain consists of a polyester bond, contains a carbon-carbon double bond at the molecular end or side chain, and does not contain an ether bond in the main chain, and the formula (In the formula, R is an alkyl group having 1 to 10 carbon atoms,
In the presence of a platinum complex catalyst, A novel method for producing a room-temperature curable polyester oligomer, characterized by carrying out the reaction at a temperature of 50 to 150°C.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6611678A JPS54156099A (en) | 1978-05-31 | 1978-05-31 | New curable polyester oligomer and its preparation |
| US05/973,889 US4191714A (en) | 1977-12-29 | 1978-12-28 | Curable polyester oligomer and a process for producing same |
| DE19782856906 DE2856906A1 (en) | 1977-12-29 | 1978-12-28 | HARDABLE POLYESTER OLIGOMER AND PROCESS FOR ITS MANUFACTURING |
| CA318,737A CA1112392A (en) | 1977-12-29 | 1978-12-28 | Curable polyester oligomer and a process for producing thereof |
| GB7850119A GB2012292B (en) | 1977-12-29 | 1978-12-28 | Curable polyester oligomer and a process for producing same |
| FR7836720A FR2413414A1 (en) | 1977-12-29 | 1978-12-28 | OLIGOMERIC POLYESTER THAT CAN BE TAKEN AND PROCESS FOR ITS PRODUCTION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6611678A JPS54156099A (en) | 1978-05-31 | 1978-05-31 | New curable polyester oligomer and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54156099A JPS54156099A (en) | 1979-12-08 |
| JPS6357452B2 true JPS6357452B2 (en) | 1988-11-11 |
Family
ID=13306582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6611678A Granted JPS54156099A (en) | 1977-12-29 | 1978-05-31 | New curable polyester oligomer and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54156099A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03155832A (en) * | 1989-11-15 | 1991-07-03 | Hitachi Ltd | Controller for electric equipment |
| JPH03156240A (en) * | 1989-11-14 | 1991-07-04 | Matsushita Electric Ind Co Ltd | Air conditioner |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5560795B2 (en) * | 2009-03-17 | 2014-07-30 | 旭硝子株式会社 | Curable composition |
| JP2012111786A (en) * | 2009-03-17 | 2012-06-14 | Asahi Glass Co Ltd | Adhesive material |
-
1978
- 1978-05-31 JP JP6611678A patent/JPS54156099A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03156240A (en) * | 1989-11-14 | 1991-07-04 | Matsushita Electric Ind Co Ltd | Air conditioner |
| JPH03155832A (en) * | 1989-11-15 | 1991-07-03 | Hitachi Ltd | Controller for electric equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54156099A (en) | 1979-12-08 |
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