KR20240047725A - Novel compound, method for preparing thereof, and composition comprising the same - Google Patents
Novel compound, method for preparing thereof, and composition comprising the same Download PDFInfo
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- KR20240047725A KR20240047725A KR1020220127110A KR20220127110A KR20240047725A KR 20240047725 A KR20240047725 A KR 20240047725A KR 1020220127110 A KR1020220127110 A KR 1020220127110A KR 20220127110 A KR20220127110 A KR 20220127110A KR 20240047725 A KR20240047725 A KR 20240047725A
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- South Korea
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- formula
- compound
- represented
- acrylate
- preparing
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract 4
- 238000002360 preparation method Methods 0.000 claims abstract 2
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims description 29
- 239000003085 diluting agent Substances 0.000 claims description 24
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 22
- 229960002479 isosorbide Drugs 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000005647 linker group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KLDXJTOLSGUMSJ-UNTFVMJOSA-N (3s,3ar,6s,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-UNTFVMJOSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-UHFFFAOYSA-N 2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound OC1COC2C(O)COC21 KLDXJTOLSGUMSJ-UHFFFAOYSA-N 0.000 description 1
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-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
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- NCNNNERURUGJAB-UHFFFAOYSA-N 3-[2,2-bis(3-prop-2-enoyloxypropoxymethyl)butoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OCCCOCC(CC)(COCCCOC(=O)C=C)COCCCOC(=O)C=C NCNNNERURUGJAB-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VGGZTNNNXAUZLB-UHFFFAOYSA-N n-ethyl-n-propan-2-ylnitrous amide Chemical compound CCN(N=O)C(C)C VGGZTNNNXAUZLB-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- LCDOENXNMQXGFS-UHFFFAOYSA-N phenoxybenzene;prop-2-enoic acid Chemical compound OC(=O)C=C.C=1C=CC=CC=1OC1=CC=CC=C1 LCDOENXNMQXGFS-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
본 발명은 신규한 화합물, 이의 제조 방법 및 이를 포함하는 조성물에 관한 것이다.The present invention relates to novel compounds, methods for their preparation and compositions containing them.
Description
본 발명은 신규한 화합물, 이의 제조 방법 및 이를 포함하는 조성물, 더 구체적으로는, 신규한 아이소소바이드 에폭시 아크릴레이트계 화합물, 이의 제조 방법, 및 이를 포함하는 조성물에 관한 것이다.The present invention relates to a novel compound, a method for producing the same, and a composition containing the same, and more specifically, to a novel isosorbide epoxy acrylate-based compound, a method for producing the same, and a composition containing the same.
현재 사용되고 있는 비스페놀계 에폭시 수지는 접착력, 기계적 물성, 내화학성이 우수하고 경화시 수축변형이 적은 장점으로 인하여 코팅, 접착제, 전기 전자, 토목 건축 등 각종 산업분야에 널리 사용되고 있다. 이러한 비스페놀계 에폭시 수지를 주재료로 하는 화학물질들은 석유에서 유래된 것으로서, 제조 및 사용 중 환경 호르몬 등의 인체에 유해한 화학물질을 발생시킨다.Currently used bisphenol-based epoxy resins are widely used in various industrial fields such as coatings, adhesives, electrical and electronics, and civil engineering due to their excellent adhesion, mechanical properties, and chemical resistance, and low shrinkage deformation when cured. These chemicals based on bisphenol-based epoxy resin are derived from petroleum and generate chemicals harmful to the human body, such as environmental hormones, during manufacturing and use.
현재 우리가 사용하고 있는 비스페놀계 에폭시를 주재료로 하는 화학물질들은 석유자원에서 유래되는 화학제품이며, 이러한 비가역 화석자원의 사용은 막대한 환경비용을 초래할 것으로 예상된다. 따라서 기존의 석유자원에서 유래되는 비스페놀계 에폭시들을 재생가능한 자원에서 얻고자 하는 연구들이 이루어지고 있으며, 가장 대표적인 것은 탄수화물계 천연원료를 공급원으로 사용하는 아이소소바이드(isosorbide, 1,4:3,6-dianhydrosorbitol), isoidide(1,4:3,6-dianhydroiditol), 및 isomannide (1,4:3,6-dianhydromannitol) 로 지칭되는 단량체들이다. 이미 비스페놀 A 대신 아이소소바이드를 적용하여 에폭시를 제조하기 위한 관련된 연구가 진행된 바 있다. (East A,Jaffe M, Zhang Y, Catalani LH. US patent 20080021209, 2008)The chemicals that we currently use based on bisphenol-based epoxy are chemical products derived from petroleum resources, and the use of these irreversible fossil resources is expected to result in enormous environmental costs. Therefore, research is being conducted to obtain bisphenol-based epoxies derived from existing petroleum resources from renewable resources, the most representative being isosorbide (1,4:3,6), which uses carbohydrate-based natural raw materials as a source. -dianhydrosorbitol), isoidide (1,4:3,6-dianhydroiditol), and isomannide (1,4:3,6-dianhydromannitol). Related research has already been conducted to produce epoxy by applying isosorbide instead of bisphenol A. (East A, Jaffe M, Zhang Y, Catalani LH. US patent 20080021209, 2008)
아이소소바이드계 에폭시, 그 중에서도, 아이소소바이드 에폭시와 아크릴산을 반응시켜 제조하는 아이소소바이드 에폭시 아크릴레이트는 무황변 특성을 가지며, 중합 시, 기계적 강도 및 열적 성질 등 물리적 성질이 우수하다는 장점이 있다. 그러나, 아이소소바이드 에폭시 아크릴레이트는 점도가 높아 단독으로 사용하기 어려운 문제점이 있다. 이에, 점도를 낮추기 위해 희석제 등의 사용이 필수적이나, 일반적인 희석제와의 상용성이 떨어져, 적합한 희석제 종류 및 사용량에 제약이 있다.Isosorbide-based epoxy, especially isosorbide epoxy acrylate, manufactured by reacting isosorbide epoxy with acrylic acid, has non-yellowing properties and has the advantage of excellent physical properties such as mechanical strength and thermal properties upon polymerization. . However, isosorbide epoxy acrylate has a problem that it is difficult to use alone due to its high viscosity. Accordingly, the use of a diluent is essential to lower the viscosity, but due to poor compatibility with general diluents, there are restrictions on the type and amount of appropriate diluent used.
이에, 아이소소바이드계 에폭시 아크릴레이트의 물리적 성질을 유지하면서, 희석제와의 상용성을 개선시키고자 하는 연구가 필요한 실정이다.Accordingly, research is needed to improve compatibility with diluents while maintaining the physical properties of isosorbide-based epoxy acrylate.
본 발명은 기계적 물성이 우수하며, 희석제와 상용성이 개선된 화합물, 이의 제조 방법 및 이를 포함하는 조성물을 제공하기 위한 것이다. The present invention is intended to provide a compound with excellent mechanical properties and improved compatibility with a diluent, a method for producing the same, and a composition containing the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by the following formula (1):
[화학식 1][Formula 1]
상기 화학식 1에서, i) R1 및 R2 중 적어도 어느 하나, 및 ii) R3 및 R4 중 적어도 어느 하나는 하기 화학식 1-1로 표시되는 연결기이고, In Formula 1, i) at least one of R 1 and R 2 , and ii) at least one of R 3 and R 4 is a linking group represented by the following Formula 1-1,
R1 내지 R4 중 하기 화학식 1-1로 표시되는 연결기가 아닌 경우는, 각각 독립적으로, 수소 또는 탄소 수 1 내지 10의 직쇄 또는 분지쇄의 알킬이고, When R 1 to R 4 are not a linking group represented by the following formula 1-1, they are each independently hydrogen or straight or branched alkyl having 1 to 10 carbon atoms;
[화학식 1-1][Formula 1-1]
상기 화학식 1-1에서, In Formula 1-1,
(*)는 상기 화학식 1과 연결되는 부분이고, (*) is the part connected to Formula 1 above,
R5는 단일 결합, 혹은 탄소 수 1 내지 5의 직쇄 또는 분지쇄의 알킬이고, R 5 is a single bond or straight or branched alkyl having 1 to 5 carbon atoms,
R6 내지 R8은, 각각 독립적으로, 탄소 수 1 내지 5의 직쇄 또는 분지쇄의 알킬렌이고,R 6 to R 8 are each independently linear or branched alkylene having 1 to 5 carbon atoms,
R9은 수소 또는 메틸이다. R 9 is hydrogen or methyl.
또한, 본 발명은, 산 무수물 및 하이드록시 알킬 아크릴레이트를 촉매 및 중합 방지제 존재 하에 반응시켜 하기 화학식 2-1로 표시되는 카르복실-에스터 아크릴레이트를 제조하는 단계(단계 1); 및 상기 카르복실-에스터 아크릴레이트와 하기 화학식 2-2로 표시되는 아이소소바이드 에폭시를 촉매 및 중합 방지제 존재 하에 반응시켜 올리고머를 제조하는 단계(단계 2);를 포함하는, 화합물 제조 방법을 제공한다:In addition, the present invention includes the steps of reacting an acid anhydride and a hydroxyalkyl acrylate in the presence of a catalyst and a polymerization inhibitor to prepare a carboxyl-ester acrylate represented by the following formula 2-1 (step 1); and reacting the carboxyl-ester acrylate with the isosorbide epoxy represented by the following formula 2-2 in the presence of a catalyst and a polymerization inhibitor to prepare an oligomer (step 2). :
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 화학식 2-1 및 2-2에서, In Formulas 2-1 and 2-2,
R1, 및 R4 내지 R9는 앞서 정의한 바와 같다.R 1 , and R 4 to R 9 are as previously defined.
또한, 본 발명은, 본 발명에 따른 화합물, 반응성 희석제 및 광개시제를 포함하는 조성물을 제공한다.The present invention also provides a composition comprising a compound according to the invention, a reactive diluent and a photoinitiator.
나아가, 본 발명은, 본 발명에 따른 화합물 유래 반복 단위를 포함하는 중합체를 제공한다.Furthermore, the present invention provides a polymer comprising repeating units derived from the compound according to the present invention.
본 발명에서, 제1, 제2 등의 용어는 다양한 구성 요소들을 설명하는데 사용되며, 상기 용어들은 하나의 구성 요소를 다른 구성 요소와 구별하기 위한 목적으로만 사용된다. In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another component.
또한, 본 명세서에서 사용되는 용어는 단지 예시적인 실시예 들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. Additionally, the terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention.
단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. Singular expressions include plural expressions unless the context clearly dictates otherwise.
본 명세서에서, "포함하다", "구비하다" 또는 "가지다" 등의 용어는 실시된 특징, 숫자, 단계, 구성 요소 또는 이들을 조합을 설명하기 위한 것이며, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 구성 요소, 이들의 조합 또는 부가 가능성을 배제하는 것은 아니다. In this specification, terms such as “comprise,” “comprise,” or “have” are used to describe implemented features, numbers, steps, components, or combinations thereof, and include one or more other features, numbers, or steps. , does not exclude the possibility of components, combinations or additions thereof.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태로 한정하는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this does not limit the present invention to the specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 10인 것이 바람직하다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸, 사이클로헥틸메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.
종래 아이소소바이드 에폭시 아크릴레이트는, 아이소소바이드 에폭시와 아크릴산을 반응시켜 형성된다. 아이소소바이드 에폭시 아크릴레이트는 점도가 높아 단독 사용하기 어려운 문제가 있어 점도를 낮추기 위한 희석제(아크릴레이트 모노머 또는 용매) 사용이 필수적이다. 상기 희석제는 대부분 소수성 물질이나, 아이소소바이드 에폭시 아크릴레이트는 분자 구조 내 아이소소바이드로부터 유래하는 고리형 에테르 구조에 기인하여 친수성 특성을 가진다. 따라서, 아이소소바이드 에폭시 아크릴레이트는 희석제와 상용성이 매우 떨어져 희석제의 사용량과 종류에 제약이 있었다.Conventionally, isosorbide epoxy acrylate is formed by reacting isosorbide epoxy and acrylic acid. Isosorbide epoxy acrylate has a high viscosity, making it difficult to use alone, so the use of a diluent (acrylate monomer or solvent) to lower the viscosity is essential. Most of the diluents are hydrophobic substances, but isosorbide epoxy acrylate has hydrophilic properties due to the cyclic ether structure derived from isosorbide in the molecular structure. Therefore, isosorbide epoxy acrylate has very poor compatibility with diluents, so there were restrictions on the amount and type of diluent used.
이에, 본 발명의 연구자들은 상기 아이소소바이드 에폭시 아크릴레이트의 분자 주쇄 내에 소수성을 발현할 수 있는 카르복실-에스터 아크릴레이트를 도입하여 희석제와 상용성이 개선되는 것을 확인함으로써 본 발명을 완성하였다. Accordingly, the researchers of the present invention completed the present invention by confirming that compatibility with a diluent was improved by introducing a carboxyl-ester acrylate capable of expressing hydrophobicity into the molecular main chain of the isosorbide epoxy acrylate.
구체적으로, 본 발명의 화합물은 하기 화학식 1로 표시되는 아이소소바이드계 화합물 내 각 고리에, 적어도 하나의 하기 화학식 1-1로 표시되는 연결기가 치환된 구조의 화합물이다:Specifically, the compound of the present invention is a compound in which each ring in the isosorbide-based compound represented by the following formula (1) is substituted with at least one linking group represented by the following formula (1-1):
[화학식 1][Formula 1]
상기 화학식 1에서, i) R1 및 R2 중 적어도 어느 하나, 및 ii) R3 및 R4 중 적어도 어느 하나는 하기 화학식 1-1로 표시되는 연결기이고, In Formula 1, i) at least one of R 1 and R 2 , and ii) at least one of R 3 and R 4 is a linking group represented by the following Formula 1-1,
R1 내지 R4 중 하기 화학식 1-1로 표시되는 연결기가 아닌 경우는, 각각 독립적으로, 수소 또는 탄소 수 1 내지 10의 직쇄 또는 분지쇄의 알킬이고, When R 1 to R 4 are not a linking group represented by the following formula 1-1, they are each independently hydrogen or straight or branched alkyl having 1 to 10 carbon atoms;
[화학식 1-1][Formula 1-1]
상기 화학식 1-1에서, In Formula 1-1,
(*)는 상기 화학식 1과 연결되는 부분이고, (*) is the part connected to Formula 1 above,
R5는 단일 결합, 혹은 탄소 수 1 내지 5의 직쇄 또는 분지쇄의 알킬이고, R 5 is a single bond or straight or branched alkyl having 1 to 5 carbon atoms,
R6 내지 R8은, 각각 독립적으로, 탄소 수 1 내지 5의 직쇄 또는 분지쇄의 알킬렌이고,R 6 to R 8 are each independently linear or branched alkylene having 1 to 5 carbon atoms,
R9은 수소 또는 메틸이다. R 9 is hydrogen or methyl.
상기 화학식 1-1로 표시되는 화합물은 소수성을 띄는 카르복실-에스터 아크릴레이트 구조를 가지면서, 카르복실 말단은 에폭시와 반응하여 연결기를 형성하는 구조이다.The compound represented by Formula 1-1 has a hydrophobic carboxyl-ester acrylate structure, and the carboxyl terminal reacts with epoxy to form a linking group.
바람직하게는, R1 및 R4는 화학식 1-1로 표시되는 연결기이고, R2 및 R3는 수소이다. Preferably, R 1 and R 4 are a linking group represented by Formula 1-1, and R 2 and R 3 are hydrogen.
바람직하게는, R5는 단일 결합이다.Preferably, R 5 is a single bond.
바람직하게는, R6 내지 R8은, 각각 독립적으로, 메틸렌, 에틸렌, 또는 n-프로필렌이다. 보다 바람직하게는, R6은 메틸렌이고, R7은 에틸렌이고, R8은 에틸렌, 또는 n-프로필렌이다. Preferably, R 6 to R 8 are each independently methylene, ethylene, or n-propylene. More preferably, R 6 is methylene, R 7 is ethylene, and R 8 is ethylene or n-propylene.
바람직하게는, 상기 화학식 1-1로 표시되는 연결기는 하기 화학식 1-2로 표시된다:Preferably, the linking group represented by Formula 1-1 is represented by the following Formula 1-2:
[화학식 1-2][Formula 1-2]
한편, 본 발명은 산 무수물 및 하이드록시 알킬 아크릴레이트를 촉매 및 중합 방지제 존재 하에 반응시켜 하기 화학식 2-1로 표시되는 카르복실-에스터 아크릴레이트를 제조하는 단계(단계 1); 및 상기 카르복실-에스터 아크릴레이트와 하기 화학식 2-2로 표시되는 아이소소바이드 에폭시를 촉매 및 중합 방지제 존재 하에 반응시켜 올리고머를 제조하는 단계(단계 2);를 포함하는, 화합물 제조 방법을 제공한다:Meanwhile, the present invention involves reacting an acid anhydride and a hydroxyalkyl acrylate in the presence of a catalyst and a polymerization inhibitor to prepare a carboxyl-ester acrylate represented by the following formula 2-1 (step 1); and reacting the carboxyl-ester acrylate with the isosorbide epoxy represented by the following formula 2-2 in the presence of a catalyst and a polymerization inhibitor to prepare an oligomer (step 2). :
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
상기 화학식 2-1 및 2-2에서, In Formulas 2-1 and 2-2,
R1, 및 R4 내지 R9는 앞서 정의한 바와 같다.R 1 , and R 4 to R 9 are as previously defined.
상기 화학식 2-1로 표시되는 화합물은 전술한 카르복실-에스터 아크릴레이트로, 일 말단에 카르복실산기를 갖고 다른 일 말단에 아크릴레이트기를 가지며, 분자 구조 내 에스터기를 가지는 화합물이다. 말단의 카르복실산기 및 아크릴레이트기는 상기 화학식 2-2로 표시되는 아이소소바이드 에폭시의 에폭시기와 반응하여 상기 화학식 1로 표시되는 화합물을 형성한다. The compound represented by Formula 2-1 is the above-mentioned carboxyl-ester acrylate, and is a compound that has a carboxylic acid group at one end and an acrylate group at the other end, and an ester group in the molecular structure. The terminal carboxylic acid group and acrylate group react with the epoxy group of the isosorbide epoxy represented by Formula 2-2 to form the compound represented by Formula 1.
본 발명의 화합물은, 상기 화학식 2-1로 표시되는 화합물 유래 구조가 분자 주쇄에 도입되어, 기존 아이소소바이드 에폭시만을 형성하는 구조에 비하여 소수성을 띄어, 소수성 희석제와 상용성이 개선될 수 있다.The compound of the present invention has a structure derived from the compound represented by Formula 2-1 introduced into the main chain of the molecule, making it more hydrophobic compared to the structure forming only the existing isosorbide epoxy, and thus compatibility with hydrophobic diluents can be improved.
본 발명의 에폭시 수지 제조 방법의 단계 1은 전술한 카르복실-에스터 아크릴레이트를 제조하는 단계이고, 단계 2는 단계 1에서 제조한 카르복실-에스터 아크릴레이트와 아이소소바이드 에폭시를 반응시켜 올리고머를 제조하는 단계이다. Step 1 of the epoxy resin production method of the present invention is to prepare the above-described carboxyl-ester acrylate, and step 2 is to prepare an oligomer by reacting the carboxyl-ester acrylate prepared in step 1 with isosorbide epoxy. This is the step.
바람직하게는, 상기 단계 1은 50 내지 120 ℃에서 진행된다. 반응 온도가 50 ℃ 미만인 경우, 반응이 진행되지 않을 수 있고, 120 ℃ 초과인 경우 원료 물질인 산 무수물 또는 하이드록시 알킬 아크킬레이트가 증발하여 원료의 손실을 초래할 수 있고, 원하지 않는 부반응이 진행될 수 있으며, 라디칼 생성으로 gel 발생 위험이 있을 수 있다. 더욱 바람직하게는, 상기 단계 1은 55 ℃ 이상, 60 ℃ 이상, 65 ℃ 이상, 또는 70 ℃ 이상이면서 115 ℃ 이하, 110 ℃ 이하, 105 ℃ 이하, 100 ℃ 이하, 또는 90 ℃ 이하에서 진행될 수 있다.Preferably, step 1 is carried out at 50 to 120 °C. If the reaction temperature is less than 50 ℃, the reaction may not proceed, and if it is higher than 120 ℃, the raw material acid anhydride or hydroxy alkyl achylate may evaporate, resulting in loss of raw materials, and unwanted side reactions may proceed. , there may be a risk of gel generation due to radical generation. More preferably, step 1 may be carried out at 55 ℃ or higher, 60 ℃ or higher, 65 ℃ or higher, or 70 ℃ or lower and 115 ℃ or lower, 110 ℃ or lower, 105 ℃ or lower, 100 ℃ or lower, or 90 ℃ or lower. .
상기 단계 1에서 사용되는 촉매는 triphenylphosphine, benzyl triethyl ammonium chloride, 및 tetramethyl ammonium chloride 등 암모늄 염 촉매를 들 수 있으며, 이를 단독 혹은 2종 이상 혼합하여 사용할 수 있다. Catalysts used in step 1 include ammonium salt catalysts such as triphenylphosphine, benzyl triethyl ammonium chloride, and tetramethyl ammonium chloride, which can be used alone or in a mixture of two or more types.
바람직하게는, 상기 단계 2는 상기 단계 2는 50 내지 120 ℃에서 진행된다. 반응 온도가 50 ℃ 미만인 경우, 반응이 진행되지 않을 수 있고, 120 ℃ 초과인 경우 부반응 또는 과도한 중합 반응이 진행될 수 있다. 더욱 바람직하게는, 상기 단계 2는 55 ℃ 이상, 60 ℃ 이상, 65 ℃ 이상, 또는 70 ℃ 이상이면서 115 ℃ 이하, 110 ℃ 이하, 105 ℃ 이하, 또는 100 ℃ 이하에서 진행될 수 있다.Preferably, step 2 is performed at 50 to 120 °C. If the reaction temperature is less than 50°C, the reaction may not proceed, and if it is higher than 120°C, side reactions or excessive polymerization may proceed. More preferably, step 2 may be carried out at 55 ℃ or higher, 60 ℃ or higher, 65 ℃ or higher, or 70 ℃ or higher and 115 ℃ or lower, 110 ℃ or lower, 105 ℃ or lower, or 100 ℃ or lower.
상기 단계 2에서 사용되는 촉매는 benzyl triethyl ammonium chloride, tetramethyl ammonium chloride, 크롬계 화합물, 및 Triethyl amine과 같은 3차 아민계 화합물을 들 수 있으며, 이를 단독 혹은 2종 이상 혼합하여 사용할 수 있다. Catalysts used in step 2 include benzyl triethyl ammonium chloride, tetramethyl ammonium chloride, chromium compounds, and tertiary amine compounds such as triethyl amine, which can be used alone or in a mixture of two or more types.
상기 단계 1 및 단계 2에서 사용되는 중합 방지제는 각각 동일하거나 상이할 수 있다. 사용 가능한 중합 방지제는 mono methyl ether hydroquinone, hydroquinone, tert-butylhydroquinone, butylated hydroxytoluene, toluhydroquinone, 4-tert-butylcatechol, butylated hydroxyanisole, propyl gallate, mono t-butyl hydroquinone, p-methoxyphenol, p-tert-butylcatechol, N,N-diethylhydroxylamine, N-nitrosoethylisopropylamine, p-benzoquinone, 2,6-Di-t-butyl-4-methylphenol, phenothiazine, 및 (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl로 구성되는 군으로부터 선택되는 1종 이상을 포함할 수 있고, 그 외, 아민계 화합물, 설폰계 화합물, 금속 화합물을 사용할 수 있다.The polymerization inhibitors used in Step 1 and Step 2 may be the same or different. Available polymerization inhibitors are mono methyl ether hydroquinone, hydroquinone, tert-butylhydroquinone, butylated hydroxytoluene, toluhydroquinone, 4-tert-butylcatechol, butylated hydroxyanisole, propyl gallate, mono t-butyl hydroquinone, p-methoxyphenol, p-tert-butylcatechol, N A group consisting of N-diethylhydroxylamine, N-nitrosoethylisopropylamine, p-benzoquinone, 2,6-Di-t-butyl-4-methylphenol, phenothiazine, and (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl It may contain one or more types selected from, and in addition, amine-based compounds, sulfone-based compounds, and metal compounds can be used.
한편, 본 발명은 상술한 본 발명의 화합물, 반응성 희석제 및 광개시제를 포함하는 에폭시 수지 조성물을 제공할 수 있다. Meanwhile, the present invention can provide an epoxy resin composition containing the above-described compound of the present invention, a reactive diluent, and a photoinitiator.
상기 반응성 희석제로는 Tripropylene glycol diacrylate, Dipropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Trimethylolpropane triacrylate, Hexanediol diacrylate, Isobornyl acrylate, Cyclic trimethylolpropane formal acrylate, 3 3,5-trimethylcyclohexyl acrylate, Tetrahydrofurfuryl acrylate, Triethylene glycol diacrylate, Polyethylene glycol diacrylate, Polypropylene glycol diacrylate, Trimethylolpropane propoxylate triacrylate, Tris(2-Hydroxy Ethyl) isocyanurate triacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Ditrimethylolpropane tetraacrylate, Pentaerythritol tetraacrylate, Benzyl methacrylate, Lauryl methacrylate, Isodecyl methaacrylate, Phenoxyethyl methacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol dimethacrylate, Ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Bisphenol A ethoxylate dimethacrylate, Polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, Ethoxylated polypropylene dimethacrylate, Caprolactone acrylate, Phenoxy benzyl acrylate, Benzyl Acrylate, Biphenylmethyl Acrylate, Lauryl Acrylate, Poly(ethylene glycol) phenyl ether acrylate, Isodecyl acrylate, 4-tert-butylcyclohexyl acrylate, Pentaerythritol triacrylate, Glyceryl propoxy triacrylate, Polypropylene glycol dimethacrylate, Trimethylolpropane trimethacrylate, Glycerol trimethacrylate, 및 Trimethylolpropane ethoxylate trimethacrylate와 대표적인 용제로 Ethyl acetate, Methyl ethyl ketone, Propylene glycol monomethyl ether acetate, 및 Toluene 등을 들 수 있으며, 이를 단독 혹은 2종 이상 혼합하여 사용할 수 있다.The reactive diluents include Tripropylene glycol diacrylate, Dipropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Trimethylolpropane triacrylate, Hexanediol diacrylate, Isobornyl acrylate, Cyclic trimethylolpropane formal acrylate, 3 3,5-trimethylcyclohexyl acrylate, Tetrahydrofurfuryl acrylate, Triethylene glycol diacrylate. late, Polyethylene glycol diacrylate, Polypropylene glycol diacrylate, Trimethylolpropane propoxylate triacrylate, Tris(2-Hydroxy Ethyl) isocyanurate triacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Ditrimethylolpropane tetraacrylate, Pentaerythritol tetraacrylate, Benzyl methacrylate, Lauryl methacrylate, Isodecyl methaacrylate, Phen oxyethyl methacrylate, 1,6-hexanediol dimethacrylate, Neopentyl glycol dimethacrylate, Ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Bisphenol A ethoxylate dimethacrylate, Polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, Ethoxylated polypropylene dimethacrylate, Caprolactone acrylate, Phenoxy benzyl acrylate, Benzyl Acrylate late, Biphenylmethyl Acrylate, Lauryl Acrylate, Poly(ethylene glycol) phenyl ether acrylate, Isodecyl acrylate, 4-tert-butylcyclohexyl acrylate, Pentaerythritol triacrylate, Glyceryl propoxy triacrylate, Polypropylene glycol dimethacrylate, Trimethylolpropane trimethacrylate, Glycerol trimethacrylate, and Trimethylolpropane ethoxylate trimethacrylate and E as a representative solvent. thyl acetate, methyl Examples include ethyl ketone, propylene glycol monomethyl ether acetate, and toluene, which can be used alone or in combination of two or more.
또한, 상기 광개시제는 Benzil dimethyl ketal, Hydroxy cyclohexyl phenyl ketone, Hydroxy dimethyl acetophenone, Methyl-(4 methylthiophenyl)-2-morpholine propanone, 2,4-Diethylthioxanthone, Ethyl-4-dimethylaminobenzoate, Benzophenone, 4-Phenylbenzophenone, 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide, 2-Hydroxy-2-methyl-1-phenyl-1-propanone 및 Methyl benzoylformate를 들 수 있으며, 이를 단독 혹은 2종 이상 혼합하여 사용할 수 있다. In addition, the photoinitiator includes Benzil dimethyl ketal, Hydroxy cyclohexyl phenyl ketone, Hydroxy dimethyl acetophenone, Methyl-(4 methylthiophenyl)-2-morpholine propanone, 2,4-Diethylthioxanthone, Ethyl-4-dimethylaminobenzoate, Benzophenone, 4-Phenylbenzophenone, 2, Examples include 4,6-Trimethylbenzoyldiphenyl phosphine oxide, 2-Hydroxy-2-methyl-1-phenyl-1-propanone, and Methyl benzoylformate, which can be used alone or in combination of two or more.
또한, 본 발명은 상술한 본 발명의 화합물 유래 반복 단위를 포함하는, 중합체를 제공한다.Additionally, the present invention provides a polymer comprising repeating units derived from the compounds of the present invention described above.
상술한 본 발명에 따른 폴리에스테르 수지는 기계적 물성이 우수하고, 희석제와 상용성이 우수하여 다양한 제품에 적용 가능하다.The polyester resin according to the present invention described above has excellent mechanical properties and excellent compatibility with diluents, so it can be applied to various products.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.
실시예 1Example 1
석신산 무수물(Succinic anhydride, 200 g)와 2-hydroxyl propyl acrylate (2-HPA, 300 g), monomethyl ether hydroquinone(MEHQ, 0.4 g)을 투입하고 70℃로 승온 후 촉매 triphenylphosphine(TPP, 5 g)를 투입하였다. 촉매 투입 후 90℃까지 승온하여 반응을 지속한다. 반응 종결시점은 IR의 산무수물 Peak(1790 cm-1)가 사라지는 시점으로 간주하였다. 반응이 종결되면 70℃까지 냉각하고 ISB epoxy(KDBM-1040, 국도화학, 356 g)를 투입하였다. 또한, 수지 색상의 변색을 최소화하고자 산화방지제 Sodium monohydrogen phosphate(0.9 g)을 투입하였다. Succinic anhydride (200 g), 2-hydroxyl propyl acrylate (2-HPA, 300 g), and monomethyl ether hydroquinone (MEHQ, 0.4 g) were added, the temperature was raised to 70°C, and the catalyst triphenylphosphine (TPP, 5 g) was added. was invested. After adding the catalyst, the temperature is raised to 90°C to continue the reaction. The end point of the reaction was considered the point at which the acid anhydride peak (1790 cm -1 ) of IR disappeared. When the reaction was completed, it was cooled to 70°C and ISB epoxy (KDBM-1040, Kukdo Chemical, 356 g) was added. In addition, the antioxidant Sodium monohydrogen phosphate (0.9 g) was added to minimize discoloration of the resin color.
70℃에서 촉매 Benzyl triethyl ammonium chloride(BTEAC, 대정화금, 4.3 g)를 투입하고 MEHQ 0.4 g을 추가 투입하였다. 이후 100℃까지 승온하고 반응을 지속하여, 산가 5이하 EEW 10,000 이상에서 반응을 종결하여, 에폭시 아크릴레이트계 화합물을 수득하였다. 제조한 에폭시 수지의 점도(60 ℃)는 2,500 cps이었다.At 70°C, the catalyst Benzyl triethyl ammonium chloride (BTEAC, Daejeong Chemical, 4.3 g) was added, and 0.4 g of MEHQ was additionally added. Afterwards, the temperature was raised to 100°C, the reaction was continued, and the reaction was terminated at an acid value of 5 or less and an EEW of 10,000 or more, thereby obtaining an epoxy acrylate-based compound. The viscosity (60°C) of the produced epoxy resin was 2,500 cps.
비교예 1Comparative Example 1
ISB epoxy(KDBM-1040, 국도화학, 500 g)와 Acrylic acid(204.5 g), sodium monohydrogen phosphate(0.7 g), 및 MEHQ(0.7 g)를 투입하고 70℃로 승온 후에 BTEAC를 투입하였다. 반응 온도 100℃에서 반응을 지속하여, 산가 5 이하, EEW 10,000 이상에서 반응을 종결하여, 하기 화학식 A로 표시되는 에폭시 아크릴레이트계 화합물을 수득하였다. 제조한 에폭시 수지의 점도(60 ℃)는 5,500 cps이었다.ISB epoxy (KDBM-1040, Kukdo Chemical, 500 g), acrylic acid (204.5 g), sodium monohydrogen phosphate (0.7 g), and MEHQ (0.7 g) were added, and after raising the temperature to 70°C, BTEAC was added. The reaction was continued at a reaction temperature of 100°C, and the reaction was terminated at an acid value of 5 or less and an EEW of 10,000 or more, to obtain an epoxy acrylate-based compound represented by the following formula (A). The viscosity (60°C) of the produced epoxy resin was 5,500 cps.
[화학식 A][Formula A]
상기 실시예 및 비교예의 에폭시 아크릴레이트계 화합물에 대해, 하기 반응성 희석제에 대한 상용성을 평가하였다. 구체적으로, 상용성 평가는 희석제 비율을 5% 단위로 올려가면서 균일하게 혼합하고, 상온(25℃)에서 상 분리 또는 백탁(비상용성으로 뿌옇게 보이는 함량) 현상 발생 여부를 관찰하였다. The epoxy acrylate-based compounds of the above Examples and Comparative Examples were evaluated for compatibility with the following reactive diluents. Specifically, in the compatibility evaluation, the diluent ratio was mixed uniformly by increasing the diluent ratio in 5% increments, and the occurrence of phase separation or cloudiness (content appearing cloudy due to incompatibility) was observed at room temperature (25°C).
예를 들어, 비교예에서 TPGDA 35의 의미는 TPGDA 35중량% 까지는 상용성이 좋아 백탁 없이 균일하게 혼합되는 반면, 40중량% 에서는 뿌옇게 되는 백탁 현상이 발생된 경우이다. 또한, 실시예 DPGDA >80의 의미는 80중량%에서 상용성이 좋아 균일하고 투명하게 혼합되는 것을 의미한다.For example, in the comparative example, the meaning of TPGDA 35 is that up to 35% by weight of TPGDA has good compatibility and is uniformly mixed without clouding, but at 40% by weight, a cloudy phenomenon occurs. In addition, Example DPGDA >80 means that it has good compatibility at 80% by weight and is mixed uniformly and transparently.
상용성 평가를 위해 사용한 반응성 희석제는 하기와 같다.The reactive diluents used for compatibility evaluation are as follows.
TPGDA: Tripropylene glycol diacrylateTPGDA: Tripropylene glycol diacrylate
DPGDA: Dipropylene glycol diacrylateDPGDA: Dipropylene glycol diacrylate
TMP(EO)3TA: Ethoxylated trimethylolpropane triacrylateTMP(EO) 3 TA: Ethoxylated trimethylolpropane triacrylate
TMPTA: Trimethylolpropane triacrylateTMPTA: Trimethylolpropane triacrylate
HDDA: Hexanediol diacrylateHDDA: Hexanediol diacrylate
EA: Ethyl acetateEA: Ethyl acetate
MEK: Methyl ethyl ketoneMEK: Methyl ethyl ketone
PGMEA(PMA): Propylene glycol monomethyl ether acetatePGMEA (PMA): Propylene glycol monomethyl ether acetate
상기 표 1에서 확인할 수 있는 바와 같이, 본 발명의 에폭시 아크릴레이트계 화합물은 비교예 1 대비 반응성 희석제와 상용성이 우수한 것을 확인할 수 있었다.As can be seen in Table 1, the epoxy acrylate-based compound of the present invention was confirmed to have excellent compatibility with the reactive diluent compared to Comparative Example 1.
실시예 2Example 2
상기 실시예 1에서 제조한 에폭시 아크릴레이트계 화합물(75 g), 및 반응성 희석제 Dipropylene glycol diacrylate(DPGDA, 25 g)를 혼합하여 점도를 15,000 cps로 맞추었다. 이후, 광 개시제(Irgacure TPO(Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide)와 Omnirad 1173(2-Hydroxy-2-methyl-1-phenyl-1-propanone)의 혼합물, 3 g)를 배합하였고, glass에 100 um로 코팅 후 UV 경화를 진행하였다(1000 mJ). 경화 후 film 형태로 시편을 제조하여 제조된 수지 조성물의 물성을 평가하였다.The epoxy acrylate compound prepared in Example 1 (75 g) and the reactive diluent dipropylene glycol diacrylate (DPGDA, 25 g) were mixed to adjust the viscosity to 15,000 cps. Afterwards, a photoinitiator (a mixture of Irgacure TPO (Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide) and Omnirad 1173 (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 3 g) was mixed. After coating the glass with 100 μm, UV curing was performed (1000 mJ). After curing, specimens were prepared in film form to evaluate the physical properties of the prepared resin composition.
비교예 2Comparative Example 2
실시예 1에서 제조한 에폭시 아크릴레이트계 화합물 대신, 비교예 1의 에폭시 아크릴레이트계 화합물을 사용한 것을 제외하고는, 실시예 2와 동일한 방법으로 수지 조성물을 제조하였다.A resin composition was prepared in the same manner as in Example 2, except that the epoxy acrylate compound of Comparative Example 1 was used instead of the epoxy acrylate compound prepared in Example 1.
비교예 3Comparative Example 3
실시예 1에서 제조한 에폭시 아크릴레이트계 화합물 대신, 상용 에폭시 수지(KDU-1100, 국도화학, 범용 Bisphenol A type epoxy acrylate)를 사용한 것을 제외하고는, 실시예 2와 동일한 방법으로 수지 조성물을 제조하였다.A resin composition was prepared in the same manner as in Example 2, except that a commercial epoxy resin (KDU-1100, Kukdo Chemical, general purpose Bisphenol A type epoxy acrylate) was used instead of the epoxy acrylate compound prepared in Example 1. .
상기 실시예 및 비교예의 수지 조성물에 대해, 하기와 같이 물성을 평가하고, 그 결과를 하기 표 2에 나타내었다. The physical properties of the resin compositions of the above examples and comparative examples were evaluated as follows, and the results are shown in Table 2 below.
(1) 인장 강도 및 인장 신율(1) Tensile strength and tensile elongation
ASTM D882의 규격에 따라 시편을 준비하였다. 상기 시편은 23℃의 온도 및 50%의 상대 습도로 조정된 항온 항습실에 24 시간 동안 방치된 후 인장 시험에 제공되었다.Specimens were prepared according to the specifications of ASTM D882. The specimen was left in a constant temperature and humidity room adjusted to a temperature of 23°C and a relative humidity of 50% for 24 hours and then subjected to a tensile test.
상기 시편에 대해 LLOYD Instruments사의 만능 시험기(UTM)를 이용하여 ASTM D882의 표준 시험법에 따라 인장 강도(MPa)와 신율을 측정하였다. ASTM D882의 표준 시험법에 의거하여 상기 시편을 양 쪽 끝에서 잡아주는 그립(grip)의 간격은 100 mm로 설정하여 크로스헤드 속도 50 mm/min의 일정한 인장 속도 하에서 수행되었다.The tensile strength (MPa) and elongation of the specimen were measured according to the standard test method of ASTM D882 using a universal testing machine (UTM) from LLOYD Instruments. According to the standard test method of ASTM D882, the gap between the grips holding the specimen at both ends was set to 100 mm, and the test was performed under a constant tensile speed of 50 mm/min crosshead speed.
(2) Pendulum hardness(2) Pendulum hardness
제조사 Biuged사의 modle BGD 509를 사용하여 ASTM D4355 규격에 의해 평가하였다. 단위는 진자 각도가 3°에 이르는 시간으로 기록하였다. 평가는 3회 진행하였고, 이들의 평균값을 나타내었다. It was evaluated according to the ASTM D4355 standard using modle BGD 509 from the manufacturer Biuged. The unit was recorded as the time for the pendulum angle to reach 3°. The evaluation was conducted three times, and the average value is shown.
(3) 연필 경도(3) Pencil hardness
ASTM D 3363에 의거하여 연필 경도를 측정하였으며, 구체적으로 연필의 각도를 45°로 고정시킨 후 시편의 표면을 6.5 mm 정도 긁어 육안으로 긁힘이 관찰되는지 평가하였으며, 연필의 강도를 바꾸어 반복 실험하였다.Pencil hardness was measured according to ASTM D 3363. Specifically, after fixing the angle of the pencil at 45°, the surface of the specimen was scratched about 6.5 mm to evaluate whether scratches were observed with the naked eye, and the test was repeated by changing the strength of the pencil.
(4) 내화학성(4) Chemical resistance
toluene, IPA, Acetone, 또는 Water를 솜에 묻혀 일정한 힘으로 100회 왕복하여 코팅 표면의 변화를 관찰하였다. 평가 전, 후 변화가 없을 경우 pass로 표기하였다. Changes in the coating surface were observed by applying toluene, IPA, Acetone, or Water to cotton and moving it back and forth 100 times with constant force. If there was no change before or after evaluation, it was marked as pass.
상기 표 2에서 확인할 수 있는 바와 같이, 본 발명에 따른 에폭시 아크릴레이계 화합물을 포함하는 수지 조성물은, 기존 에폭시 아크릴레이트 수지와 동등 또는 우수한 물성을 가지는 것을 확인하였다.As can be seen in Table 2, the resin composition containing the epoxy acrylate-based compound according to the present invention was confirmed to have physical properties equivalent to or superior to existing epoxy acrylate resins.
Claims (12)
[화학식 1]
상기 화학식 1에서, i) R1 및 R2 중 적어도 어느 하나, 및 ii) R3 및 R4 중 적어도 어느 하나는 하기 화학식 1-1로 표시되는 연결기이고,
R1 내지 R4 중 하기 화학식 1-1로 표시되는 연결기가 아닌 경우는, 각각 독립적으로, 수소 또는 탄소 수 1 내지 10의 직쇄 또는 분지쇄의 알킬이고,
[화학식 1-1]
상기 화학식 1-1에서,
(*)는 상기 화학식 1과 연결되는 부분이고,
R5는 단일 결합, 혹은 탄소 수 1 내지 5의 직쇄 또는 분지쇄의 알킬이고,
R6 내지 R8은, 각각 독립적으로, 탄소 수 1 내지 5의 직쇄 또는 분지쇄의 알킬렌이고,
R9은 수소 또는 메틸이다.
Compound represented by Formula 1:
[Formula 1]
In Formula 1, i) at least one of R 1 and R 2 , and ii) at least one of R 3 and R 4 is a linking group represented by the following Formula 1-1,
When R 1 to R 4 are not a linking group represented by the following formula 1-1, they are each independently hydrogen or straight or branched alkyl having 1 to 10 carbon atoms;
[Formula 1-1]
In Formula 1-1,
(*) is the part connected to Formula 1 above,
R 5 is a single bond or straight or branched alkyl having 1 to 5 carbon atoms,
R 6 to R 8 are each independently linear or branched alkylene having 1 to 5 carbon atoms,
R 9 is hydrogen or methyl.
R1 및 R4는 화학식 1-1로 표시되는 연결기이고, R2 및 R3는 수소인,
화합물.
According to paragraph 1,
R 1 and R 4 are linking groups represented by Formula 1-1, and R 2 and R 3 are hydrogen,
compound.
R5는 단일 결합인,
화합물.
According to paragraph 1,
R 5 is a single bond,
compound.
R6 내지 R8은, 각각 독립적으로, 메틸렌, 에틸렌, 또는 n-프로필렌인,
화합물.
According to paragraph 1,
R 6 to R 8 are each independently methylene, ethylene, or n-propylene,
compound.
상기 화학식 1-1로 표시되는 연결기는 하기 화학식 1-2로 표시되는,
화합물:
[화학식 1-2]
According to paragraph 1,
The linking group represented by Formula 1-1 is represented by Formula 1-2 below,
compound:
[Formula 1-2]
상기 카르복실-에스터 아크릴레이트와 하기 화학식 2-2로 표시되는 아이소소바이드 에폭시를 촉매 및 중합 방지제 존재 하에 반응시켜 올리고머를 제조하는 단계(단계 2);를 포함하는,
화합물 제조 방법:
[화학식 2-1]
[화학식 2-2]
상기 화학식 2-1 및 2-2에서,
R1, 및 R4 내지 R9는 제1항에서 정의한 바와 같다.
Preparing a carboxyl-ester acrylate represented by the following formula 2-1 by reacting an acid anhydride and a hydroxyalkyl acrylate in the presence of a catalyst and a polymerization inhibitor (step 1); and
Comprising: preparing an oligomer by reacting the carboxyl-ester acrylate with the isosorbide epoxy represented by the following formula 2-2 in the presence of a catalyst and a polymerization inhibitor (step 2);
Compound Preparation Method:
[Formula 2-1]
[Formula 2-2]
In Formulas 2-1 and 2-2,
R 1 , and R 4 to R 9 are as defined in clause 1.
상기 단계 1은 50 내지 120 ℃에서 진행되는,
화합물 제조 방법.
According to clause 6,
Step 1 is carried out at 50 to 120 ° C.
Method of preparing the compound.
상기 단계 2는 50 내지 120 ℃에서 진행되는,
화합물 제조 방법.
According to clause 6,
Step 2 is carried out at 50 to 120 ° C.
Method of preparing the compound.
조성물.
Comprising a compound according to claims 1 to 5, a reactive diluent and a photoinitiator,
Composition.
반응성 희석제는 Tripropylene glycol diacrylate, Dipropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Trimethylolpropane triacrylate, Hexanediol diacrylate, Ethyl acetate, Methyl ethyl ketone, 및 Propylene glycol monomethyl ether acetate로 구성되는 군으로부터 선택되는 1종 이상을 포함하는,
조성물.
According to clause 9,
The reactive diluent includes one or more selected from the group consisting of Tripropylene glycol diacrylate, Dipropylene glycol diacrylate, Ethoxylated trimethylolpropane triacrylate, Trimethylolpropane triacrylate, Hexanediol diacrylate, Ethyl acetate, Methyl ethyl ketone, and Propylene glycol monomethyl ether acetate.
Composition.
반응성 희석제는 조성물 100 중량부 기준 5 내지 40 중량부로 포함되는,
조성물.
According to clause 9,
The reactive diluent is included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the composition.
Composition.
Priority Applications (1)
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KR1020220127110A KR20240047725A (en) | 2022-10-05 | 2022-10-05 | Novel compound, method for preparing thereof, and composition comprising the same |
Publications (1)
Publication Number | Publication Date |
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KR20240047725A true KR20240047725A (en) | 2024-04-12 |
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Country | Link |
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2022
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