KR20210029159A - Terminal (meth)acrylate polycarbonate oligomer - Google Patents
Terminal (meth)acrylate polycarbonate oligomer Download PDFInfo
- Publication number
- KR20210029159A KR20210029159A KR1020207037565A KR20207037565A KR20210029159A KR 20210029159 A KR20210029159 A KR 20210029159A KR 1020207037565 A KR1020207037565 A KR 1020207037565A KR 20207037565 A KR20207037565 A KR 20207037565A KR 20210029159 A KR20210029159 A KR 20210029159A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- group
- polycarbonate oligomer
- terminal
- acrylate
- Prior art date
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 69
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 7
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- -1 n-octyl group Chemical group 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 238000005809 transesterification reaction Methods 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000002516 radical scavenger Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 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 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013076 target substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WURUICCPWMHUFA-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)-3-methylphenyl]propan-2-yl]-2-methylphenoxy]ethanol Chemical compound C1=C(OCCO)C(C)=CC(C(C)(C)C=2C=C(C)C(OCCO)=CC=2)=C1 WURUICCPWMHUFA-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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ICQFAQGXJAVDED-UHFFFAOYSA-N benzene-1,4-diol;4-(methylamino)phenol Chemical compound OC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ICQFAQGXJAVDED-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical class [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GCLVVFYKIZYIIL-UHFFFAOYSA-N (2-butylphenyl)-diphenylborane Chemical compound CCCCC1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 GCLVVFYKIZYIIL-UHFFFAOYSA-N 0.000 description 1
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 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
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-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
- GUFOLAUVJTWOBK-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]dodecyl]phenoxy]ethanol Chemical compound OCCOC1=CC=C(C=C1)C(CCCCCCCCCCC)C1=CC=C(C=C1)OCCO GUFOLAUVJTWOBK-UHFFFAOYSA-N 0.000 description 1
- TZIYYPHSIYMLQN-UHFFFAOYSA-N 2-[4-[1-[4-(2-hydroxyethoxy)phenyl]ethyl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)C1=CC=C(OCCO)C=C1 TZIYYPHSIYMLQN-UHFFFAOYSA-N 0.000 description 1
- ZMKBETOAFQAZNU-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)phenyl]-4-methylpentan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)(CC(C)C)C1=CC=C(OCCO)C=C1 ZMKBETOAFQAZNU-UHFFFAOYSA-N 0.000 description 1
- RYFDAZYNMLFWKG-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)phenyl]butan-2-yl]phenoxy]ethanol Chemical compound C=1C=C(OCCO)C=CC=1C(C)(CC)C1=CC=C(OCCO)C=C1 RYFDAZYNMLFWKG-UHFFFAOYSA-N 0.000 description 1
- MFBRWKCKAGAJAJ-UHFFFAOYSA-N 2-[4-[[4-(2-hydroxyethoxy)phenyl]methyl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1CC1=CC=C(OCCO)C=C1 MFBRWKCKAGAJAJ-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000005010 aminoquinolines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- PDYNXWPJDVOHDW-UHFFFAOYSA-N bis(3-methylphenyl) carbonate Chemical compound CC1=CC=CC(OC(=O)OC=2C=C(C)C=CC=2)=C1 PDYNXWPJDVOHDW-UHFFFAOYSA-N 0.000 description 1
- PACOTQGTEZMTOT-UHFFFAOYSA-N bis(ethenyl) carbonate Chemical compound C=COC(=O)OC=C PACOTQGTEZMTOT-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ANHGITKPRSIRHT-UHFFFAOYSA-N cyclohexyl phenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1CCCCC1 ANHGITKPRSIRHT-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
Images
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
본 발명은 UV 경화형 하드코팅제 등에 사용되는 UV 경화형 (메타)아크릴 수지의 원료로서, 다관능 (메타)아크릴 모노머와의 상용성과, 용매 용해성이 우수한 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 제공하는 것을 과제로 한다.
상기 과제를 해결하기 위해, 본 발명은 식(1) 및／또는 (2)로 표시되고, 중량 평균 분자량(Mw)이 500 이상 10,000 이하의 범위인 것을 특징으로 하는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 제공한다.The present invention is to provide a terminal (meth)acrylate polycarbonate oligomer having excellent compatibility with a polyfunctional (meth)acrylic monomer and excellent solvent solubility as a raw material for a UV curable (meth)acrylic resin used in a UV curable hard coating agent, etc. Make it an assignment.
In order to solve the above problems, the present invention is represented by formulas (1) and/or (2), and the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less. Oligomer.
Description
본 발명은 용매 용해성이 양호한 말단 (메타)아크릴레이트 폴리카보네이트 올리고머에 관한 것이다.The present invention relates to a terminal (meth)acrylate polycarbonate oligomer having good solvent solubility.
수지재료는 경량이고 저렴하며 가공성도 우수하다는 등의 장점으로부터, 엔지니어링 플라스틱으로서 범용되고 있는데, 유리나 금속에 비해 표면의 경도, 내찰상성, 내약품성 등이 떨어지기 때문에, 그대로 대체재료로서 채용되는 경우는 없다. 수지재료의 이들 결점을 개량하기 위해, 수지 표면에 기재의 수지와는 다른 소재의 수지제 박막을 형성하여, 외적 요인으로부터 기재의 수지를 보호하고, 표면 개질을 도모하는 하드코팅 처리가 일반적으로 행하여지고 있다. 이 하드코팅층의 형성은 기재의 수지 표면에 하드코팅제를 도포하여 건조한 후, 필요에 따라 전자선, 자외선(UV) 등의 방사선을 조사하여 경화하는 시스템이 채용되고 있다(예를 들면, 특허문헌 1, 2). 이중에서도, UV 경화성 수지를 사용한 UV 경화형 하드코팅제가 종래의 하드코팅제에 비해 저온으로 단시간에 처리가 가능해지기 때문에, 생산성이 높아 다양한 용도로 전개되고 있다. Resin materials are widely used as engineering plastics because of their advantages such as light weight, inexpensiveness, and excellent processability, but their surface hardness, scratch resistance, and chemical resistance are lower than that of glass or metal. none. In order to improve these drawbacks of the resin material, a resin thin film of a material different from the resin of the base material is formed on the surface of the resin to protect the resin of the base material from external factors, and a hard coating treatment to promote surface modification is generally performed. Is losing. For the formation of this hard coating layer, a system is employed in which a hard coating agent is applied to the resin surface of the substrate, dried, and then cured by irradiating radiation such as electron beams and ultraviolet rays (UV), if necessary (for example, Patent Document 1, 2). Among these, since the UV curable hard coating agent using a UV curable resin can be processed in a short time at a low temperature compared to the conventional hard coating agent, the productivity is high and it is developed for various purposes.
이 UV 경화형 하드코팅제는 주성분으로서 펜타에리스리톨계 (메타)아크릴레이트 등의 다관능 (메타)아크릴 모노머가 사용되기 때문에, 배합되는 성분은 이들 다광능 (메타)아크릴 모노머와의 상용성이 높은 것이 요구되고 있다. Since this UV-curable hard coating agent uses polyfunctional (meth)acrylic monomers such as pentaerythritol-based (meth)acrylate as the main component, it is required that the components to be blended have high compatibility with these multi-photoactive (meth)acrylic monomers. Has become.
본 발명은 전술한 사정을 배경으로 하여 이루어진 것으로서, UV 경화형 하드코팅제 등에 사용되는 UV 경화형 (메타)아크릴 수지의 원료로서, 다관능 (메타)아크릴 모노머와의 상용성과, 용매 용해성이 우수한 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 제공하는 것을 목적으로 한다. The present invention has been made against the above-described circumstances, as a raw material for a UV-curable (meth)acrylic resin used in a UV-curable hard coating agent, etc., and has excellent compatibility with a polyfunctional (meth)acrylic monomer, and excellent solvent solubility. ) An object of the present invention is to provide an acrylate polycarbonate oligomer.
본 발명자들은 전술한 과제 해결을 위해 예의 검토한 결과, 아래 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트에 있어서, 중량 평균 분자량(Mw)이 특정 범위인 올리고머가 다관능 (메타)아크릴 모노머와의 상용성이 우수하고, 용매 용해성도 양호한 것을 발견하고, 본 발명을 완성하였다. As a result of intensive examination for solving the aforementioned problems, the present inventors found that in the terminal (meth)acrylate polycarbonate represented by the following formulas (1) and/or (2), oligomers having a weight average molecular weight (Mw) in a specific range Was found to be excellent in compatibility with the polyfunctional (meth)acrylic monomer, and the solvent solubility was also good, and the present invention was completed.
본 발명은 아래와 같다. The present invention is as follows.
1. 아래 식(1) 및／또는 (2)로 표시되고, 중량 평균 분자량(Mw)이 500 이상 10,000 이하의 범위인 것을 특징으로 하는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머. 1. A terminal (meth)acrylate polycarbonate oligomer represented by the following formulas (1) and/or (2), wherein the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.
(식(1), (2) 중, R1∼R4는 각각 독립적으로 수소원자, 탄소원자수 1∼8의 알킬기, 탄소수 5∼12의 시클로알킬기, 탄소원자수 1∼8의 알콕시기, 또는 탄소원자수 6∼12의 방향족 탄화수소기를 나타내고, R5는 각각 독립적으로 수소원자 또는 메틸기를 나타내며, R6, R7은 각각 독립적으로 수소원자 또는 탄소원자수 1∼14의 알킬기를 나타내고, X는 탄소원자수 2∼4의 알킬렌기를 나타내며, n은 1 이상의 정수이다. 단, R6 및 R7의 탄소원자수의 합계는 14 이하이고, X에 결합해 있는 2개의 산소원자는 X의 동일 탄소원자에는 결합하지 않는다.)(In formulas (1) and (2), R 1 to R 4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon source. Represents an aromatic hydrocarbon group of 6 to 12 embroidery, R 5 each independently represents a hydrogen atom or a methyl group, R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and X is 2 carbon atoms Represents an alkylene group of ∼4, and n is an integer greater than or equal to 1. However, the total number of carbon atoms of R 6 and R 7 is 14 or less, and the two oxygen atoms bonded to X are not bonded to the same carbon atom of X. I don't.)
본 발명에 의한 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는 중량 평균 분자량(Mw)이 500 이상 10,000 이하의 범위인 것으로부터, 펜타에리스리톨계 (메타)아크릴레이트 등의 다관능 (메타)아크릴 모노머와의 상용성이 우수하고, 용매 용해성도 양호하기 때문에, UV 경화형 하드코팅제의 원료로서 최적으로, UV 경화에 의해 평활한 도막 형성이 가능하다고 하는 공업적으로 유리한 효과를 발휘한다. The terminal (meth)acrylate polycarbonate oligomer according to the present invention has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less, so that it is mixed with a polyfunctional (meth)acrylic monomer such as pentaerythritol (meth)acrylate. Since it has excellent compatibility and good solvent solubility, it is optimal as a raw material for a UV-curable hard coating agent and exhibits an industrially advantageous effect that a smooth coating film can be formed by UV curing.
도 1은 실시예 1에서 합성한 말단 (메타)아크릴레이트 폴리카보네이트 올리고머(1c)의 1H－NMR 스펙트럼 차트이다.
도 2는 실시예 2에서 합성한 말단 (메타)아크릴레이트 폴리카보네이트 올리고머(1d)의 1H－NMR 스펙트럼 차트이다. 1 is a 1 H-NMR spectrum chart of a terminal (meth)acrylate polycarbonate oligomer (1c) synthesized in Example 1. FIG.
2 is a 1 H-NMR spectrum chart of a terminal (meth)acrylate polycarbonate oligomer (1d) synthesized in Example 2. FIG.
아래에 본 발명의 말단 (메타)아크릴레이트 폴리카보네이트 올리고머에 대해서 상세하게 설명한다. Hereinafter, the terminal (meth)acrylate polycarbonate oligomer of the present invention will be described in detail.
본 발명의 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는 아래 반응식에 예시하는 바와 같이, 식(A)로 표시되는 폴리카보네이트 올리고머와, (메타)아크릴산 클로라이드와 같은 (메타)아크릴화제의 반응에 의해 얻어지는, 중량 평균 분자량(Mw)이 500 이상 10,000 이하의 범위인, 아래 식(1) 및／또는 아래 식(2)로 표시되는 화합물이다.The terminal (meth)acrylate polycarbonate oligomer of the present invention is obtained by reaction of a polycarbonate oligomer represented by formula (A) and a (meth)acrylate agent such as (meth)acrylic acid chloride, as illustrated in the reaction formula below. , The weight average molecular weight (Mw) is a compound represented by the following formula (1) and/or the following formula (2) in the range of 500 or more and 10,000 or less.
(반응식 중 R1∼R7, X, n의 정수는 전술한 식(1), (2)와 동일하다.)(In the reaction formula , the integers of R 1 to R 7 , X, and n are the same as those of the aforementioned formulas (1) and (2).)
＜식(A)로 표시되는 폴리카보네이트 올리고머에 대해서＞<About the polycarbonate oligomer represented by formula (A)>
본 발명의 말단 (메타)아크릴레이트 폴리카보네이트 올리고머의 화학구조에 대해서는, 그의 합성원료인 아래 식(A)로 표시되는 폴리카보네이트 올리고머를 상세하게 설명함으로써 그의 설명으로 한다. 즉, 식(A) 중 R1∼R4, R6, R7, X, n의 구체적인 예, 바람직한 화학기나 그의 치환기 등에 대해서는, 본 발명의 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 나타내는, 식(1) 또는 (2) 중 R1∼R7, X, n과 동일하다. The chemical structure of the terminal (meth)acrylate polycarbonate oligomer of the present invention is described in detail by describing in detail the polycarbonate oligomer represented by the following formula (A), which is a raw material for its synthesis. That is, for specific examples of R 1 to R 4 , R 6 , R 7 , X, n in formula (A), preferred chemical groups and substituents thereof, the formula (meth) acrylate polycarbonate oligomer of the present invention is shown. It is the same as R 1 to R 7 , X and n in (1) or (2).
(식(A) 중 R1∼R4, R6, R7, X, n의 정수는 전술한 식(1), (2)와 동일하다.)(In the formula (A) , the integers of R 1 to R 4 , R 6 , R 7 , X, and n are the same as those of the aforementioned formulas (1) and (2).)
상기 식(A)에 있어서, R1, R2, R3 및 R4 중 어느 하나가 탄소원자수 1∼8의 알킬기인 경우, 알킬기로서는 바람직하게는 탄소원자수 1∼4의 직쇄상, 분지쇄상의 알킬기이고, 구체적으로는, 예를 들면 메틸기, 에틸기, n－프로필기, 이소프로필기, 이소부틸기 등을 들 수 있다. 이러한 알킬기에는 본 발명의 효과를 손상시키지 않는 범위에서, 예를 들면 페닐기, 탄소원자수 1∼4의 알콕시기 등의 치환기를 가지고 있어도 된다.In the above formula (A), when any one of R 1 , R 2 , R 3 and R 4 is an alkyl group having 1 to 8 carbon atoms, the alkyl group is preferably a linear or branched chain having 1 to 4 carbon atoms. It is an alkyl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, etc. are mentioned, for example. Such an alkyl group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms, within a range that does not impair the effects of the present invention.
R1, R2, R3 및 R4 중 어느 하나가 탄소원자수 5∼12의 시클로알킬기인 경우, 시클로알킬기로서는 바람직하게는 탄소원자수 5∼7의 시클로알킬기이고, 구체적으로는, 예를 들면 시클로헥실기, 시클로펜틸기, 시클로헵틸기 등을 들 수 있다. 이러한 시클로알킬기에는 본 발명의 효과를 손상시키지 않는 범위에서, 예를 들면 직쇄 또는 분지쇄상의 탄소원자수 1∼4의 알킬기, 탄소원자수 1∼4의 알콕시기, 페닐기 등의 치환기를 가지고 있어도 된다.When any one of R 1 , R 2 , R 3 and R 4 is a cycloalkyl group having 5 to 12 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms, and specifically, for example, cyclo Hexyl group, cyclopentyl group, cycloheptyl group, etc. are mentioned. Such a cycloalkyl group may have a substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group as long as the effect of the present invention is not impaired.
또한, R1, R2, R3 및 R4 중 어느 하나가 탄소원자수 1∼8의 알콕시기인 경우, 알콕시기로서는 바람직하게는 탄소원자수 1∼4의 직쇄상, 분지쇄상의 알콕시기이고, 구체적으로는, 예를 들면 메톡시기, 에톡시기 등을 들 수 있다. 이러한 알콕시기에는 본 발명의 효과를 손상시키지 않는 범위에서, 예를 들면 페닐기, 탄소원자수 1∼4의 알콕시기 등의 치환기를 가지고 있어도 된다.In addition, when any one of R 1 , R 2 , R 3 and R 4 is an alkoxy group having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and specifically Examples of examples include a methoxy group and an ethoxy group. Such an alkoxy group may have, for example, a substituent such as a phenyl group and an alkoxy group having 1 to 4 carbon atoms within the range not impairing the effects of the present invention.
또한, R1, R2, R3 및 R4 중 어느 하나가 탄소원자수 6∼12의 방향족 탄화수소기인 경우, 방향족 탄화수소기로서는, 구체적으로는, 예를 들면 페닐기, 나프틸기 등을 들 수 있다. 이러한 방향족 탄화수소기에는 본 발명의 효과를 손상시키지 않는 범위에서, 예를 들면 탄소원자수 1∼4의 알킬기 및／또는 탄소원자수 1∼4의 알콕시기가 1∼3 정도 치환되어 있어도 된다.In addition, when any one of R 1 , R 2 , R 3 and R 4 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, specifically, examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Such an aromatic hydrocarbon group may be substituted with about 1 to 3 carbon atoms, for example, an alkyl group having 1 to 4 carbon atoms and/or an alkoxy group having 1 to 4 carbon atoms within the range not impairing the effects of the present invention.
R1, R2, R3 및 R4의 치환기가 결합하는 위치는 그 벤젠 고리에 결합하는 산소원자에 대해 오르토 위치가 바람직하다.The position at which the substituent of R 1 , R 2 , R 3 and R 4 is bonded is preferably an ortho position with respect to the oxygen atom bonded to the benzene ring.
상기 식(A)에 있어서, R6 및 R7 중 어느 하나가 탄소원자수 1∼14의 알킬기인 경우, 알킬기로서는 바람직하게는 탄소원자수 1∼12의 직쇄상, 분지쇄상의 알킬기이고, 구체적으로는, 예를 들면 메틸기, 에틸기, n－프로필기, 이소프로필기, n－부틸기, 이소부틸기, n－펜틸기, n－헥실기, n－헵틸기, n－옥틸기, n－노닐기, n－데실기, n－운데실기, n－도데실기 등을 들 수 있다. 단, R6 및 R7의 탄소원자수의 합계는 14 이하여야만 한다. In the formula (A), when any one of R 6 and R 7 is an alkyl group having 1 to 14 carbon atoms, the alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and specifically , For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group , n-decyl group, n-undecyl group, and n-dodecyl group. However, the total number of carbon atoms of R 6 and R 7 must be 14 or less.
상기 식(A)에 있어서, X는 구체적으로는 에틸렌기, n－프로필렌기, 프로판－1,2－디일기, n－부틸렌기, 부탄－1,3－디일기, 부탄－1,2－디일기, 부탄－2,3－디일기를 나타내며, 그중에서도 에틸렌기, n－프로필렌기, 프로판－1,2－디일기, n－부틸렌기가 바람직하고, 에틸렌기, 프로판－1,2－디일기가 보다 바람직하며, 에틸렌기가 특히 바람직하다. In the formula (A), X is specifically an ethylene group, n-propylene group, propane-1,2-diyl group, n-butylene group, butane-1,3-diyl group, butane-1,2- Represents a diyl group and a butane-2,3-diyl group, among which ethylene group, n-propylene group, propane-1,2-diyl group, and n-butylene group are preferable, and ethylene group, propane-1,2-di Diary is more preferable, and ethylene group is particularly preferable.
식(A)로 표시되는 폴리카보네이트 올리고머는 종래 공지의 임의의 제조방법에 의해 제조되는 것을 사용할 수 있다. 구체적으로는, 예를 들면 계면중합법, 용융 에스테르 교환법, 피리딘법, 환상 카보네이트 화합물의 개환중합법, 프리폴리머의 고상 에스테르 교환법 등을 들 수 있다. 그중에서도, 계면중합법, 용융 에스테르 교환법, 프리폴리머의 고상 에스테르 교환법을 사용하는 것이 산업상 유리하다. 이들 중에서도, 포스겐을 사용하지 않는 용융 에스테르 교환법이나, 용융 에스테르 교환법에 의한 프리폴리머의 고상 에스테르 교환법이 특히 바람직하다. 상기 제조방법은 아래 식(B)로 표시되는 디히드록시 화합물과 탄산 에스테르 형성제를 사용해서 행하여진다. The polycarbonate oligomer represented by the formula (A) can be prepared by any conventionally known production method. Specifically, for example, an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, a solid-phase transesterification method of a prepolymer, and the like can be mentioned. Among them, it is industrially advantageous to use an interfacial polymerization method, a melt transesterification method, and a solid-state transesterification method of a prepolymer. Among these, a melt transesterification method that does not use phosgene and a solid-state transesterification method of a prepolymer by a melt transesterification method are particularly preferred. The above production method is carried out using a dihydroxy compound represented by the following formula (B) and a carbonate ester forming agent.
(식(B) 중 R1∼R4, R6, R7, X의 정수는 전술한 식(1), (2)와 동일하다.)(In formula (B) , the integers of R 1 to R 4 , R 6 , R 7 , and X are the same as those of the aforementioned formulas (1) and (2).)
＜식(B)로 표시되는 디히드록시 화합물에 대해서＞<About the dihydroxy compound represented by formula (B)>
식(B)로 표시되는 디히드록시 화합물로서는, 구체적으로는, 예를 들면 비스(4－(2－히드록시에톡시)페닐)메탄, 2,2－비스(4－(2－히드록시에톡시)페닐)프로판, 2,2－비스(4－(2－히드록시에톡시)－3－메틸페닐)프로판, 1,1－비스(4－(2－히드록시에톡시)페닐)에탄, 2,2－비스(4－(2－히드록시에톡시)페닐)－4－메틸펜탄, 2,2－비스(4－(2－히드록시에톡시)페닐)부탄, 1,1－비스(4－(2－히드록시에톡시)페닐)도데칸 등을 들 수 있다.Specific examples of the dihydroxy compound represented by formula (B) include bis(4-(2-hydroxyethoxy)phenyl)methane and 2,2-bis(4-(2-hydroxy). Oxy)phenyl)propane, 2,2-bis(4-(2-hydroxyethoxy)-3-methylphenyl)propane, 1,1-bis(4-(2-hydroxyethoxy)phenyl)ethane, 2 ,2-bis(4-(2-hydroxyethoxy)phenyl)-4-methylpentane, 2,2-bis(4-(2-hydroxyethoxy)phenyl)butane, 1,1-bis(4 -(2-hydroxyethoxy)phenyl)dodecane, etc. are mentioned.
중합반응 시에 이러한 디히드록시 화합물은 단독으로도, 2종 이상을 임의의 비율로 혼합해서 사용해도 된다. During the polymerization reaction, these dihydroxy compounds may be used alone or in combination of two or more in an arbitrary ratio.
＜탄산 에스테르 형성제에 대해서＞<About Carbonic Acid Ester Forming Agent>
식(B)로 표시되는 디히드록시 화합물과 반응시키는 탄산 에스테르 형성제로서는, 구체적으로는, 예를 들면 디페닐카보네이트, 디톨릴카보네이트, 비스(m－크레실)카보네이트 등의 탄산디아릴, 디메틸카보네이트, 디에틸카보네이트, 디시클로헥실카보네이트 등의 탄산디알킬, 메틸페닐카보네이트, 에틸페닐카보네이트, 시클로헥실페닐카보네이트 등의 탄산알킬아릴 또는 디비닐카보네이트, 디이소프로페닐카보네이트, 디프로페닐카보네이트 등의 탄산디알케닐 등의 탄산디에스테르류를 들 수 있다. 또한, 포스겐 등의 디할로겐화 카르보닐 화합물 등이나 트리포스겐도 들 수 있다. 이들 중에서 탄산디아릴이 바람직하고, 디페닐카보네이트가 특히 바람직하다. Examples of the carbonate ester forming agent reacted with the dihydroxy compound represented by formula (B) include, for example, diaryl carbonate, dimethyl carbonate such as diphenyl carbonate, ditolyl carbonate, and bis(m-cresyl) carbonate. Carbonic acid such as dialkyl carbonate, such as carbonate, diethyl carbonate, and dicyclohexyl carbonate, alkyl aryl carbonate such as methylphenyl carbonate, ethylphenyl carbonate, and cyclohexylphenyl carbonate, or divinyl carbonate, diisopropenyl carbonate, and dipropenyl carbonate. Carbonic acid diesters, such as dialkenyl, are mentioned. Moreover, dihalogenated carbonyl compounds, such as phosgene, etc., and triphosgene are also mentioned. Among these, diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.
＜용융 에스테르 교환법에 대해서＞<About the melt transesterification method>
식(A)로 표시되는 폴리카보네이트 올리고머의 제조방법으로서 용융 에스테르 교환법에 대해서 설명한다. A melt transesterification method will be described as a method for producing the polycarbonate oligomer represented by formula (A).
용융 에스테르 교환반응의 방법으로서는, 식(B)로 표시되는 디히드록시 화합물과, 탄산 에스테르 형성제로서 디페닐카보네이트를 사용하는 경우에는, 촉매의 존재하, 상압 또는 감압의 불활성 가스 분위기에서 가열하면서 교반하고, 생성되는 페놀을 유출(溜出)시켜서 행하여진다. 통상, 식(B)로 표시되는 디히드록시 화합물과 탄산 에스테르 형성제의 혼합 비율이나, 에스테르 교환반응 시의 감압도를 조정하여, 목적하는 분자량 및 말단 수산기량을 조정한, 식(A)로 표시되는 폴리카보네이트 올리고머를 얻을 수 있다. As a method of melt transesterification, in the case of using a dihydroxy compound represented by the formula (B) and diphenyl carbonate as the carbonate ester forming agent, heating in an inert gas atmosphere at atmospheric pressure or reduced pressure in the presence of a catalyst. It is carried out by stirring and distilling out the generated phenol. Usually, by adjusting the mixing ratio of the dihydroxy compound represented by the formula (B) and the carbonate ester forming agent or the degree of pressure reduction during the transesterification reaction, the desired molecular weight and the amount of terminal hydroxyl groups are adjusted, according to the formula (A). The polycarbonate oligomer shown can be obtained.
식(A)로 표시되는 폴리카보네이트 올리고머를 얻기 위해, 식(B)로 표시되는 디히드록시 화합물과 탄산 에스테르 형성제의 혼합 비율은, 식(B)로 표시되는 디히드록시 화합물 1 몰에 대해 탄산 에스테르 형성제를 통상 0.2∼1.0 몰배, 바람직하게는 0.25∼0.95 몰배, 더욱 바람직하게는 0.3∼0.90 몰배를 사용한다. In order to obtain the polycarbonate oligomer represented by the formula (A), the mixing ratio of the dihydroxy compound represented by the formula (B) and the carbonate ester forming agent is based on 1 mole of the dihydroxy compound represented by the formula (B). The carbonate ester forming agent is usually 0.2 to 1.0 mole times, preferably 0.25 to 0.95 mole times, and more preferably 0.3 to 0.90 mole times.
용융 에스테르 교환반응 시에 반응속도를 높이기 위해, 필요에 따라 에스테르 교환 촉매가 사용된다. 에스테르 교환 촉매로서는 특별히 제한은 없고, 예를 들면 리튬, 나트륨, 세슘의 수산화물, 탄산염, 탄산수소 화합물 등의 무기 알칼리금속 화합물, 알코올레이트, 유기 카르복실산염 등의 유기 알칼리금속 화합물 등의 알칼리금속 화합물；베릴륨, 마그네슘 등의 수산화물, 탄산염 등의 무기 알칼리토류금속 화합물, 알코올레이트, 유기 카르복실산염 등의 유기 알칼리토류금속 화합물 등의 알칼리토류금속 화합물；테트라메틸붕소, 테트라에틸붕소, 부틸트리페닐붕소 등의 나트륨염, 칼슘염, 마그네슘염 등의 염기성 붕소 화합물；트리에틸포스핀, 트리－n－프로필포스핀 등의 3가의 인화합물, 또는 이들 화합물로부터 유도되는 4급 포스포늄염 등의 염기성 인화합물；테트라메틸암모늄 히드록시드, 테트라에틸암모늄 히드록시드, 테트라부틸암모늄 히드록시드 등의 염기성 암모늄 화합물；4－아미노피리딘, 2－디메틸아미노이미다졸, 아미노퀴놀린 등 아민계 화합물 등의 공지의 에스테르 교환 촉매를 사용할 수 있다. 그중에서도, 알칼리금속 화합물이 바람직하고, 특히 탄산세슘, 수산화세슘 등의 세슘 화합물이 바람직하다. In order to increase the reaction rate during the melt transesterification reaction, a transesterification catalyst is used if necessary. The transesterification catalyst is not particularly limited, and examples include inorganic alkali metal compounds such as lithium, sodium, and cesium hydroxides, carbonates, and hydrogen carbonate compounds, and alkali metal compounds such as organic alkali metal compounds such as alcoholates and organic carboxylate salts. Alkaline earth metal compounds such as inorganic alkaline earth metal compounds such as hydroxides and carbonates such as beryllium and magnesium, and organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron, tetraethylboron, butyltriphenylboron Basic boron compounds such as sodium salts, calcium salts, magnesium salts, etc.; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, or basic phosphorus such as quaternary phosphonium salts derived from these compounds Compounds; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; Known amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinoline Transesterification catalysts can be used. Among them, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferable.
촉매의 사용량은 촉매 잔류물에 의한 생성 올리고머의 품질상 문제가 생기지 않는 범위에서 사용되며, 촉매의 종류에 따라 적합한 첨가량이 상이하기 때문에 일률적으로는 말할 수 없으나, 개략, 예를 들면 식(B)로 표시되는 디히드록시 화합물 1 몰에 대해 통상 0.05∼100 μ몰, 바람직하게는 0.08∼50 μ몰, 보다 바람직하게는 0.1∼20 μ몰, 더욱 바람직하게는 0.1∼5 μ몰이다. 촉매는 그대로 첨가해도 되고, 용매에 용해하여 첨가해도 되며, 용매로서는 예를 들면 물, 페놀 등의 반응에 영향을 미치지 않는 것이 바람직하다. The amount of catalyst used is within a range that does not cause problems in the quality of the oligomer produced by catalyst residues, and since the appropriate amount of addition is different depending on the type of catalyst, it cannot be said unequivocally. It is usually 0.05 to 100 µmol, preferably 0.08 to 50 µmol, more preferably 0.1 to 20 µmol, and still more preferably 0.1 to 5 µmol with respect to 1 mol of the displayed dihydroxy compound. The catalyst may be added as it is or may be added by dissolving it in a solvent, and it is preferable that the solvent does not affect the reaction such as water or phenol.
용융 에스테르 교환반응의 반응조건은 온도는 통상 120∼360℃의 범위, 바람직하게는 150∼280℃의 범위, 보다 바람직하게는 180∼260℃의 범위이다. 반응온도가 지나치게 낮으면 에스테르 교환반응이 진행되지 않고, 반응온도가 높으면 분해반응 등의 부반응이 진행되기 때문에 바람직하지 않다. 반응은 바람직하게는 감압하에서 행하여진다. 반응압력은 반응온도에 있어서 원료인 탄산 에스테르 형성제가 계외로 유출되지 않고, 페놀 등의 부생물을 유출할 수 있는 압력인 것이 바람직하다. 이러한 반응조건에 있어서 반응은 통상 0.5∼10시간 정도에서 완결한다. The reaction conditions for the melt transesterification reaction are usually in the range of 120 to 360°C, preferably in the range of 150 to 280°C, and more preferably in the range of 180 to 260°C. If the reaction temperature is too low, the transesterification reaction does not proceed, and if the reaction temperature is high, side reactions such as decomposition reactions proceed, which is not preferable. The reaction is preferably carried out under reduced pressure. The reaction pressure is preferably a pressure at the reaction temperature at which the carbonic acid ester forming agent, which is a raw material, does not flow out of the system, and by-products such as phenol can flow out. Under these reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.
＜(메타)아크릴화에 대해서＞<About (meth)acrylate>
상기 반응식에 있어서 예시하는 바와 같이, 본 발명의 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는, 식(A)로 표시되는 폴리카보네이트 올리고머와, (메타)아크릴산 클로라이드와 같은 (메타)아크릴화제의 반응에 의해 얻어진다.As exemplified in the above reaction formula, the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) of the present invention is a polycarbonate oligomer represented by formula (A), and (meta ) Obtained by the reaction of a (meth)acrylicating agent such as acrylic acid chloride.
(메타)아크릴화제로서는, 구체적으로는, 예를 들면 아크릴산 클로라이드, 메타크릴산 클로라이드, 아크릴산, 메타크릴산 등을 들 수 있다.Specific examples of the (meth)acrylate agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid, and methacrylic acid.
(메타)아크릴화제의 사용량은 식(1)로 표시되는 양쪽 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 얻는 경우에는, 식(A)로 표시되는 폴리카보네이트 올리고머의 전체 말단 히드록실기에 대해 (메타)아크릴화제를 통상 1.0∼2.5 몰배, 바람직하게는 1.1∼2.0 몰배, 더욱 바람직하게는 1.15∼1.5 몰배 사용한다. The amount of the (meth)acrylicating agent to be used is (meth)acrylate polycarbonate oligomer represented by formula (1), with respect to all terminal hydroxyl groups of the polycarbonate oligomer represented by formula (A). ) The acrylate agent is usually used in an amount of 1.0 to 2.5 mole times, preferably 1.1 to 2.0 mole times, and more preferably 1.15 to 1.5 mole times.
식(2)로 표시되는 한쪽 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 얻는 경우에는, 식(A)로 표시되는 폴리카보네이트 올리고머의 전체 말단 히드록실기에 대해 (메타)아크릴화제를 통상 0.5∼1.5 몰배, 바람직하게는 0.55∼1.25 몰배, 더욱 바람직하게는 0.6∼1.0 몰배 사용한다. In the case of obtaining one terminal (meth)acrylate polycarbonate oligomer represented by formula (2), a (meth)acrylate agent is usually 0.5 to 1.5 with respect to all terminal hydroxyl groups of the polycarbonate oligomer represented by formula (A). The mole times, preferably 0.55 to 1.25 mole times, more preferably 0.6 to 1.0 mole times, are used.
예를 들면, (메타)아크릴산 클로라이드를 사용하여 식(A)로 표시되는 폴리카보네이트 올리고머를 아크릴화하는 경우, 클로라이드 이온이 염화수소의 형태로 발생하기 때문에, 염화수소 포착제를 병용하는 것이 바람직하다. 염화수소 포착제로서는 염기성 물질이라면 사용할 수 있다. 무기 염기성 물질로서는 알칼리금속의 탄산염이나 탄산수소염 등을 사용할 수 있다. 유기 염기성 물질로서는 3급 아민류를 사용할 수 있다. 3급 아민류로서는, 예를 들면 트리메틸아민, 트리에틸아민, 트리－n－프로필아민, 트리이소프로필아민, 트리부틸아민, N－메틸－디에틸아민, N－에틸－디메틸아민, N－에틸－디아밀아민, N,N－디이소프로필에틸아민, N,N－디메틸－시클로헥실아민, N,N－디에틸－시클로헥실아민 등의 지방족 아민；N,N－디메틸아닐린, N,N－디에틸아닐린 등의 방향족 아민；피리딘, 피콜린, N,N－디메틸아미노피리딘 등의 헤테로 고리 아민；1,8－디아자비시클로[5.4.0]운데카－7－엔, 1,5－디아자비시클로[4.3.0]논－5－엔 등의 지환식 아민 등을 들 수 있다. For example, in the case of acrylating the polycarbonate oligomer represented by the formula (A) using (meth)acrylic acid chloride, since chloride ions are generated in the form of hydrogen chloride, it is preferable to use a hydrogen chloride scavenger together. As the hydrogen chloride scavenger, it can be used as long as it is a basic substance. As the inorganic basic substance, a carbonate or hydrogen carbonate of an alkali metal can be used. Tertiary amines can be used as the organic basic substance. As tertiary amines, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl- Aliphatic amines such as diamylamine, N,N-diisopropylethylamine, N,N-dimethyl-cyclohexylamine, and N,N-diethyl-cyclohexylamine; N,N-dimethylaniline, N,N- Aromatic amines such as diethylaniline; Heterocyclic amines such as pyridine, picoline, and N,N-dimethylaminopyridine; 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-dia Alicyclic amines, such as zabicyclo[4.3.0]non-5-ene, etc. are mentioned.
염화수소 포착제의 사용량으로서는, 통상은 사용되는 (메타)아크릴화제의 몰 수에 대해 0.8∼10 배몰이고, 바람직하게는 0.9∼8 배몰, 특히 바람직하게는 1.0∼7 배몰 정도이다. 염화수소 포착제가 (메타)아크릴화제의 몰 수에 대해 0.8배 미만이면, 발생하는 염화수소를 완전히 포착하지 못하여, 원료의 식(A)로 표시되는 폴리카보네이트 올리고머나, 목적물인 식(1) 또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 분해해 버려, 목적물의 순도 저하를 일으킬 우려가 있다. 또한, 염화수소 포착제가 (메타)아크릴화제의 몰 수에 대해 10 배몰을 초과하면, 염화수소 포착제의 제거가 번잡해질 뿐 아니라 경제적이지 못하기 때문에 바람직하지 않다. The amount of the hydrogen chloride scavenger to be used is usually 0.8 to 10 times mol, preferably 0.9 to 8 times mol, particularly preferably about 1.0 to 7 times mol with respect to the number of moles of the (meth)acrylate used. When the hydrogen chloride scavenger is less than 0.8 times the number of moles of the (meth)acrylic agent, the generated hydrogen chloride cannot be completely captured, and thus the polycarbonate oligomer represented by the formula (A) of the raw material or the target product of the formula (1) or (2) The terminal (meth)acrylate polycarbonate oligomer represented by) is decomposed, and there is a concern that the purity of the target product may be lowered. In addition, when the hydrogen chloride scavenger exceeds 10 times the mole number of the (meth)acrylic agent, it is not preferable because the removal of the hydrogen chloride scavenger becomes complicated and not economical.
이 (메타)아크릴화의 반응에 있어서 사용되는 용매는 사용되는 원료 등을 균일하게 혼합할 수 있는 용매면 되고, 구체적으로는, 염화메틸렌과 같은 할로겐화 탄화수소나 테트라히드로푸란, 디옥산, 클로로벤젠 등을 들 수 있다. 용매의 사용량은 특별히 한정되지 않으나, 통상 식(A)로 표시되는 폴리카보네이트 올리고머에 대해 0.5∼100 중량부이고, 바람직하게는 1∼50 중량부, 특히 바람직하게는 2∼10 중량부이다. The solvent used in this (meth)acrylate reaction may be a solvent capable of uniformly mixing the raw materials used, and specifically, halogenated hydrocarbons such as methylene chloride, tetrahydrofuran, dioxane, chlorobenzene, etc. Can be lifted. The amount of the solvent to be used is not particularly limited, but is usually 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 2 to 10 parts by weight, based on the polycarbonate oligomer represented by the formula (A).
(메타)아크릴화의 반응은 비교적 낮은 온도에서 실시되어, 통상은 －50∼100℃, 바람직하게는 －30∼80℃, 특히 바람직하게는 －15∼60℃이다. 반응온도가 100℃를 초과하면 부반응이 일어나 목적물의 수율 저하로 이어진다. 또한, －50℃ 미만에서는 반응속도가 느려져 소요시간이 지나치게 걸려 경제적이지 못하다. The reaction of (meth)acrylate is carried out at a relatively low temperature, and is usually -50 to 100°C, preferably -30 to 80°C, and particularly preferably -15 to 60°C. When the reaction temperature exceeds 100°C, side reactions occur, leading to a decrease in the yield of the target product. In addition, below -50°C, the reaction rate becomes slow and the time required is excessive, which is not economical.
반응순서로서는, 사전에, 식(A)로 표시되는 폴리카보네이트 올리고머와 (메타)아크릴화제를 용매 중에서 혼합하고, 거기에 염화수소 포착제를 첨가하는 방법이나, 먼저, 식(A)로 표시되는 폴리카보네이트 올리고머와 염화수소 포착제를 용매 중에서 혼합하고, 거기에 (메타)아크릴화제를 첨가하는 방법이 있다. 이들 방법에 있어서, 나중에 첨가하는 염화수소 포착제나 (메타)아크릴화제는 용매에 희석한 상태에서 사용해도 된다. As a reaction sequence, a method of mixing the polycarbonate oligomer represented by the formula (A) and a (meth) acrylate in a solvent, and adding a hydrogen chloride scavenger thereto, or, firstly, the polycarbonate oligomer represented by the formula (A). There is a method of mixing a carbonate oligomer and a hydrogen chloride scavenger in a solvent, and adding a (meth)acrylate agent thereto. In these methods, a hydrogen chloride scavenger or a (meth)acrylating agent added later may be used in a state diluted with a solvent.
또한, 반응 시에 중합금지제로서, 예를 들면 하이드로퀴논, 하이드로퀴논모노메틸에테르, 페노티아진, 2,6－디－tert－부틸－4－메틸페놀(BHT) 등을 첨가해도 된다. In addition, as a polymerization inhibitor during the reaction, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT) or the like may be added.
＜(메타)아크릴화의 후처리와 정제에 대해서＞<About post-treatment and purification of (meth)acrylate>
(메타)아크릴화 반응에 있어서는 염화수소 포착제인 염기성 물질은 과잉으로 첨가되는 경우가 많고, 특히 유기 염기성 물질은 목적물인 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머와 함께 유기 용매 중에 잔존하여, 착색·분해 등의 바람직하지 않은 현상을 일으키기 쉽기 때문에, 반응 후의 세정작업에서 제거해 두는 것이 바람직하다. 유기 염기성 물질을 세정 제거하기 위해서는 산성 물질의 수용액으로 세정하는 것이 바람직하다. 사용하는 산성 물질로서는 특별히 한정되는 것은 아니나, 무기계 산성 물질로서는, 예를 들면 염산, 황산, 질산 등이 있고, 유기계 산성 물질로서는, 예를 들면 포름산, 초산, 프로피온산, 부티르산 등의 카르복실산；메탄설폰산, 트리플루오로메탄설폰산, p－톨루엔설폰산 등의 설폰산 등이 있다. 그중에서도, 산성도가 낮은 유기성 산성 물질이 보다 바람직하다. 염화수소 포착제를 제거한 후에는 계속해서 수세를 실시하는 것이 바람직하다. In the (meth)acrylate reaction, a basic substance as a hydrogen chloride scavenger is often added in excess, and in particular, an organic basic substance is a terminal (meth)acrylate polycarbonate oligomer represented by formulas (1) and/or (2), which are the target substances. It remains in an organic solvent together with it, and since it is easy to cause undesirable phenomena such as coloring and decomposition, it is preferable to remove it in the washing operation after the reaction. In order to remove the organic basic substance by washing, it is preferable to wash it with an aqueous solution of an acidic substance. The acidic substance to be used is not particularly limited, but examples of the inorganic acidic substance include hydrochloric acid, sulfuric acid, nitric acid, and the like. Examples of the organic acidic substance include carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid; methane And sulfonic acids such as sulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Among them, organic acidic substances with low acidity are more preferable. After removing the hydrogen chloride scavenger, it is preferable to continue washing with water.
얻어진 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는, 용해되어 있는 용액 중에 빈용매를 첨가함으로써 침전물로서 얻는 방법 등이 바람직하다. 상기 빈용매로서는, 구체적으로는, 예를 들면 메탄올, 에탄올, 프로판올 등의 탄소수 1∼6의 지방족 알코올 용매 또는 상기 지방족 알코올 용매와 물의 혼합물을 들 수 있다. The obtained terminal (meth)acrylate polycarbonate oligomer represented by formulas (1) and/or (2) is preferably a method of obtaining as a precipitate by adding a poor solvent to the dissolved solution. Specific examples of the poor solvent include an aliphatic alcohol solvent having 1 to 6 carbon atoms such as methanol, ethanol, and propanol, or a mixture of the aliphatic alcohol solvent and water.
＜말단 (메타)아크릴레이트 폴리카보네이트 올리고머에 대해서＞<About the terminal (meth)acrylate polycarbonate oligomer>
본 발명의 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머의 바람직한 화합물에 대해서, 아래에 구체적인 예를 나타낸다. A specific example is shown below about the preferable compound of the terminal (meth)acrylate polycarbonate oligomer represented by Formula (1) and/or (2) of this invention.
식(1)로 표시되는 양쪽 말단 (메타)아크릴레이트 폴리카보네이트 올리고머의 바람직한 화합물은 아래와 같다. 식(1a)∼(1d) 중 n은 1 이상의 정수인데, 중량 평균 분자량(Mw)은 500 이상 10,000 이하의 범위이다. Preferred compounds of both terminal (meth)acrylate polycarbonate oligomers represented by formula (1) are as follows. In formulas (1a) to (1d), n is an integer of 1 or more, and the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.
식(2)로 표시되는 한쪽 말단 (메타)아크릴레이트 폴리카보네이트 올리고머의 바람직한 화합물은 아래와 같다. 식(2a)∼(2d) 중 n은 1 이상의 정수인데, 중량 평균 분자량(Mw)은 500 이상 10,000 이하의 범위이다. Preferred compounds of one terminal (meth)acrylate polycarbonate oligomer represented by formula (2) are as follows. In formulas (2a) to (2d), n is an integer of 1 or more, and the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.
본 발명의 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는, 중량 평균 분자량(Mw)이 500 이상 10,000 이하의 범위이고, 그중에서도 1,000 이상 8,000 이하의 범위가 바람직하며, 2,000 이상 6,000 이하의 범위가 보다 바람직하다. 중량 평균 분자량(Mw)이 이 범위 내이면, 유기 용매에 대해 양호한 용해성이 얻어지기 때문에 바람직하다. The terminal (meth)acrylate polycarbonate oligomer represented by formulas (1) and/or (2) of the present invention has a weight average molecular weight (Mw) of 500 or more and 10,000 or less, and among them, 1,000 or more and 8,000 or less. It is preferable, and the range of 2,000 or more and 6,000 or less is more preferable. When the weight average molecular weight (Mw) is within this range, it is preferable because good solubility in an organic solvent is obtained.
또한, 본 발명의 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머를 UV 경화형 하드코팅제의 성분으로서 사용하는 경우에는, 주성분인 펜타에리스리톨계 (메타)아크릴레이트 등의 다관능 (메타)아크릴 모노머와의 상용성이 우수하기 때문에, UV 경화에 의해 평활한 도막 형성이 가능하다고 하는 공업적으로 유리한 효과를 발휘한다. In addition, when the terminal (meth)acrylate polycarbonate oligomer represented by formulas (1) and/or (2) of the present invention is used as a component of a UV-curable hard coating agent, pentaerythritol-based (meth)acrylate as the main component Since it is excellent in compatibility with polyfunctional (meth)acrylic monomers such as, it exhibits an industrially advantageous effect that a smooth coating film can be formed by UV curing.
본 발명의 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는 UV 경화형 하드코팅제의 원료 이외에, 3D 프린터의 조형용 재료 원료나 에폭시 수지 등의 열경화 수지의 개질제로서 유용하다. The terminal (meth)acrylate polycarbonate oligomer represented by the formulas (1) and/or (2) of the present invention is a material for molding 3D printers, in addition to a raw material for a UV-curable hard coating agent, or a modifier for a thermosetting resin such as an epoxy resin. It is useful as
실시예 Example
아래에 본 발명을 실시예에 의해 구체적으로 설명하는데, 본 발명은 이들 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
또한, 아래의 예에 있어서의 중량 평균 분자량(Mw)은 겔 침투 크로마토그래피에 의해 측정하였다. 그 분석방법은 아래와 같다. In addition, the weight average molecular weight (Mw) in the following example was measured by gel permeation chromatography. The analysis method is as follows.
＜분석방법＞ <Analysis method>
1. 겔 침투 크로마토그래피 측정1. Gel permeation chromatography measurement
(올리고머의 분석)(Analysis of oligomers)
장치：도소 주식회사 제조 HLC-8320GPCEquipment: manufactured by Tosoh Corporation HLC-8320GPC
유량：0.35 ㎖/min, 이동상：테트라히드로푸란, 주입량：10 ㎕Flow rate: 0.35 ml/min, mobile phase: tetrahydrofuran, injection amount: 10 µl
칼럼：TSKgel guardcolumn SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-N×3개Column: TSKgel guard column SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-N×3
검출기：RI,Detector: RI,
해석방법：폴리스티렌 환산의 상대 분자량으로 한다. Analysis method: It is taken as the relative molecular weight in terms of polystyrene.
폴리스티렌 표품：도소 주식회사 제조 A-500,A-2500,A-5000,F-1,F-2,F-4Polystyrene Standard: A-500,A-2500,A-5000,F-1,F-2,F-4 manufactured by Tosoh Corporation
(폴리머의 분석)(Analysis of polymer)
장치：도소 주식회사 제조 HLC-8320GPCEquipment: HLC-8320GPC manufactured by Tosoh Corporation
유량：1.0 ㎖/min, 이동상：테트라히드로푸란, 주입량：100 ㎕Flow rate: 1.0 ml/min, mobile phase: tetrahydrofuran, injection amount: 100 µl
칼럼：TSKgel guardcolumn HXL-L TSKgel G2000HXL×2개＋TSKgel G3000HXL＋TSKgel G4000HXLColumn: TSKgel guard column HXL-L TSKgel G2000HXL x 2 + TSKgel G3000HXL + TSKgel G4000HXL
검출기：RI, Detector: RI,
해석방법：폴리스티렌 환산의 상대 분자량으로 한다. Analysis method: It is taken as the relative molecular weight in terms of polystyrene.
폴리스티렌 표품：도소 주식회사 제조 PStQuick E,F(E：F-40,F-4,A-5000,A-1000, F：F-20,F-2,A-2500,A-500)Polystyrene Standard: PStQuick E, F (E: F-40, F-4, A-5000, A-1000, F: F-20, F-2, A-2500, A-500) manufactured by Tosoh Corporation
2. 말단 히드록실 농도의 측정2. Measurement of terminal hydroxyl concentration
1H－NMR을 사용하여 TCE(1,1,1,2-테트라클로로에탄)를 내부 표준으로 하여, 비스페놀 A, 비스페놀 C를 표품으로 사용하여 TCE와의 중량비의 검량선을 작성하였다. 이 검량선으로부터 페놀 말단 중량을 구하는 방법으로 정량하였다. Using 1 H-NMR, using TCE (1,1,1,2-tetrachloroethane) as an internal standard, bisphenol A and bisphenol C were used as standards, and a calibration curve of the weight ratio with TCE was prepared. It quantified by the method of determining the phenol terminal weight from this calibration curve.
장치：BRUKER사 제조 AscendTM 400Equipment: Ascend TM 400 manufactured by BRUKER
측정조건：실온, 적산횟수 120회Measurement conditions: room temperature, number of integrations 120 times
3. 화학구조의 동정3. Identification of chemical structure
상기 「2.」와 동일한 장치를 사용하여 1H－NMR 측정에 의해 실시하였다. It carried out by 1 H-NMR measurement using the same apparatus as said "2.".
＜참고예 1＞ 폴리카보네이트 올리고머(A－a)의 합성<Reference Example 1> Synthesis of polycarbonate oligomer (A-a)
온도계, 교반기, 냉각기를 구비한 4구 플라스크에 2,2－비스(4－(2－히드록시에톡시)－3－메틸페닐)프로판 388.6 g(1.1 몰), 디페닐카보네이트 169.2 g(0.8 몰)을 넣고, 반응용기를 질소치환한 후, 110℃에서 0.09% 탄산세슘 수용액 0.82 g을 첨가하였다. 200℃까지 승온한 후, 감압도를 0.3 ㎪로 조정하여, 2시간, 생성된 페놀을 유출시키면서 반응하여, 반응 종료액 383.4 g을 얻었다. 2,2-bis(4-(2-hydroxyethoxy)-3-methylphenyl)propane 388.6 g (1.1 mol), diphenyl carbonate 169.2 g (0.8 mol) in a 4-neck flask equipped with a thermometer, stirrer, and cooler After the reaction vessel was replaced with nitrogen, 0.82 g of 0.09% cesium carbonate aqueous solution was added at 110°C. After heating up to 200 degreeC, the degree of reduced pressure was adjusted to 0.3 kPa, and reacted for 2 hours while distilling out the generated phenol to obtain 383.4 g of a reaction termination liquid.
이어서, 얻어진 반응 종료액 372.6 g을 온도계, 교반기, 냉각기를 구비한 4구 플라스크에 넣고, 톨루엔 745.2 g에 용해시켜, 추가로 메탄올 2235.6 g을 첨가하고, 실온에서 30분 교반하였다. 30분 정치하여 분리된 상층의 용액을 빼내고, 얻어진 하층 용액에 톨루엔 558.9 g, 메탄올 2235.6 g을 첨가하여, 동일하게 교반, 정치, 상층 용액의 빼내기 작업을 2회 행하였다. 그 후, 용제를 농축함으로써, 폴리카보네이트 올리고머(A－a) 193.5 g을 얻었다. 얻어진 폴리카보네이트 올리고머의 중량 평균 분자량은 4630(겔 침투 크로마토그래피), 말단 히드록실 농도는 0.67 mmol／g이었다. Next, 372.6 g of the obtained reaction termination liquid was put into a four-necked flask equipped with a thermometer, a stirrer and a cooler, dissolved in 745.2 g of toluene, and 2235.6 g of methanol was further added, followed by stirring at room temperature for 30 minutes. The solution of the upper layer separated by standing for 30 minutes was removed, and 558.9 g of toluene and 2235.6 g of methanol were added to the obtained lower layer solution, and stirring, standing, and extraction of the upper layer solution were performed twice in the same manner. Then, 193.5 g of polycarbonate oligomers (A-a) were obtained by concentrating the solvent. The weight average molecular weight of the obtained polycarbonate oligomer was 4630 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.67 mmol/g.
＜실시예 1＞ 말단 아크릴레이트 폴리카보네이트 올리고머(1c)의 합성<Example 1> Synthesis of terminal acrylate polycarbonate oligomer (1c)
온도계, 교반기, 냉각기를 구비한 4구 플라스크에, 참고예 1에서 얻어진 폴리카보네이트 올리고머(A－a) 80.3 g을 넣고, 반응용기를 질소치환한 후, 아크릴산 클로라이드 7.3 g(0.08 몰), 디클로로메탄 120.5 g, 메토퀴논 4.0 ㎎을 질소 기류하에서 첨가하였다. 10℃에서 트리에틸아민 10.9 g(0.11 몰)과 디클로로메탄 40.2 g의 혼합용액을 2시간에 걸쳐 첨가하였다. 추가로 10℃에서 1시간 교반을 계속한 후, 물 825 g과 메탄올 960 g을 첨가하고, 1시간 교반 후, 정치하여 분리된 상층의 용액을 빼내고, 추가로 메탄올 960 g을 첨가하여, 교반하였다. 1시간 교반 후, 정치하여 분리된 상층의 용액을 빼내고, 추가로 메탄올 320 g을 첨가하여, 교반하였다. 2시간 교반 후, 침전물을 여과 분별하고, 건조하여, 분말상의 말단 아크릴레이트 폴리카보네이트 올리고머(1c) 79.3 g을 취득하였다. To a 4-neck flask equipped with a thermometer, stirrer, and cooler, 80.3 g of the polycarbonate oligomer (A-a) obtained in Reference Example 1 was added, and the reaction vessel was replaced with nitrogen, and then 7.3 g (0.08 mol) of acrylic acid chloride, dichloromethane. 120.5 g and 4.0 mg of metoquinone were added under a nitrogen stream. At 10°C, a mixed solution of 10.9 g (0.11 mol) of triethylamine and 40.2 g of dichloromethane was added over 2 hours. After further stirring at 10° C. for 1 hour, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the solution of the upper layer separated by standing was removed, and 960 g of methanol was further added and stirred. . After stirring for 1 hour, the solution of the upper layer separated by standing still was removed, and further 320 g of methanol was added, followed by stirring. After stirring for 2 hours, the precipitate was separated by filtration and dried to obtain 79.3 g of a powdery terminal acrylate polycarbonate oligomer (1c).
얻어진 말단 아크릴레이트 폴리카보네이트 올리고머(1c)의 중량 평균 분자량은 5,211이었다(겔 침투 크로마토그래피). 1H－NMR의 분석결과로부터, 상기 식(1c)에 나타내어지는 양쪽 말단 아크릴레이트 폴리카보네이트 올리고머인 것을 확인하였다. 도 1에, 얻어진 말단 아크릴레이트 폴리카보네이트 올리고머(1c)의 1H－NMR 스펙트럼 차트를 나타낸다. The weight average molecular weight of the obtained terminal acrylate polycarbonate oligomer (1c) was 5,211 (gel permeation chromatography). From the analysis result of 1 H-NMR, it was confirmed that it was the both terminal acrylate polycarbonate oligomer represented by the said formula (1c). In Figure 1 shows a 1 H-NMR spectrum chart of the obtained polycarbonate oligomer terminated acrylate (1c).
얻어진 말단 아크릴레이트 폴리카보네이트 올리고머(1c) 2.0 g과 시클로헥사논 10.0 g을 혼합한 바, 투명한 용액이 얻어졌다. 또한, 다관능 아크릴레이트인 펜타에리스리톨테트라아크릴레이트 8.0 g, 이르가큐어(184) 0.5 g을 혼합한 바, 투명한 용액이 얻어졌다.When 2.0 g of the obtained terminal acrylate polycarbonate oligomer (1c) and 10.0 g of cyclohexanone were mixed, a transparent solution was obtained. Further, when 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of Irgacure (184) were mixed, a transparent solution was obtained.
얻어진 말단 아크릴레이트 폴리카보네이트 올리고머(1c)는 시클로헥사논 등의 유기 용매에 양호한 용해성을 나타내고, 또한, 다관능 아크릴레이트인 펜타에리스리톨테트라아크릴레이트와의 상용성이 우수한 것이 명확해졌다. It has become clear that the obtained terminal acrylate polycarbonate oligomer (1c) exhibits good solubility in organic solvents such as cyclohexanone, and has excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate.
＜실시예 2＞ 말단 메타크릴레이트 폴리카보네이트 올리고머(1d)의 합성<Example 2> Synthesis of terminal methacrylate polycarbonate oligomer (1d)
온도계, 교반기, 냉각기를 구비한 4구 플라스크에, 참고예 1에서 얻어진 폴리카보네이트 올리고머(A－a) 96 g을 넣고, 반응용기를 질소치환한 후, 메타크릴산 클로라이드 8.5 g(0.08 몰), 디클로로메탄 120.4 g, 메토퀴논 4.6 ㎎을 질소 기류하에서 첨가하였다. 10℃에서 트리에틸아민 10.9 g(0.11 몰)을 30분에 걸쳐 첨가하였다. 추가로 10℃에서 2시간 교반을 계속한 후, 물 825 g과 메탄올 960 g을 첨가하고, 1시간 교반 후, 정치하여 분리된 상층의 용액을 빼내고, 추가로 메탄올 960 g을 첨가하여, 교반하였다. 2시간 교반 후, 침전물을 여과 분별하고, 추가로 얻어진 웨트 케이크를 메탄올 960 g 중에 재분산시키는 세정공정을 실시하였다. 그 후, 침전물을 여과 분별하고, 건조하여, 분말상의 말단 메타크릴레이트 폴리카보네이트 올리고머(1d) 56.1 g을 취득하였다. To a four-necked flask equipped with a thermometer, a stirrer, and a cooler, 96 g of the polycarbonate oligomer (A-a) obtained in Reference Example 1 was added, and the reaction vessel was nitrogen-substituted, and then 8.5 g (0.08 mol) of methacrylic acid chloride, 120.4 g of dichloromethane and 4.6 mg of metoquinone were added under a nitrogen stream. At 10° C., 10.9 g (0.11 mol) of triethylamine were added over 30 minutes. After further stirring at 10° C. for 2 hours, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the solution of the upper layer separated by standing was removed, and 960 g of methanol was further added and stirred. . After stirring for 2 hours, the precipitate was separated by filtration, and a washing step was performed in which the wet cake obtained further was redispersed in 960 g of methanol. Thereafter, the precipitate was separated by filtration and dried to obtain 56.1 g of a powdery terminal methacrylate polycarbonate oligomer (1d).
얻어진 말단 메타크릴레이트 폴리카보네이트 올리고머(1d)의 중량 평균 분자량은 4,734였다(겔 침투 크로마토그래피). 1H－NMR의 분석결과로부터, 상기 식(1d)에 나타내어지는 양쪽 말단 메타크릴레이트 폴리카보네이트 올리고머인 것을 확인하였다. 도 2에, 얻어진 말단 메타크릴레이트 폴리카보네이트 올리고머(1d)의 1H－NMR 스펙트럼 차트를 나타낸다. The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (1d) was 4,734 (gel permeation chromatography). From the analysis result of 1 H-NMR, it was confirmed that it was the both terminal methacrylate polycarbonate oligomer represented by the said formula (1d). In Figure 2, shows the 1 H-NMR spectrum chart of the obtained methacrylate terminated polycarbonate oligomer (1d).
얻어진 말단 메타크릴레이트 폴리카보네이트 올리고머(1d) 2.0 g과 시클로헥사논 10.0 g을 혼합한 바, 투명한 용액이 얻어졌다. 또한, 다관능 아크릴레이트인 펜타에리스리톨테트라아크릴레이트 8.0 g, 이르가큐어(184) 0.5 g을 혼합한 바, 투명한 용액이 얻어졌다. When 2.0 g of the obtained terminal methacrylate polycarbonate oligomer (1d) and 10.0 g of cyclohexanone were mixed, a transparent solution was obtained. Further, when 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of Irgacure (184) were mixed, a transparent solution was obtained.
얻어진 말단 메타크릴레이트 폴리카보네이트 올리고머(1d)는 시클로헥사논 등의 유기 용매에 양호한 용해성을 나타내고, 또한, 다관능 아크릴레이트인 펜타에리스리톨테트라아크릴레이트와의 상용성이 우수한 것이 명확해졌다. It has become clear that the obtained terminal methacrylate polycarbonate oligomer (1d) exhibits good solubility in organic solvents such as cyclohexanone, and has excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate.
＜비교예 1＞ 말단 디아크릴폴리카보네이트의 합성<Comparative Example 1> Synthesis of terminal diacrylic polycarbonate
온도계, 교반기, 냉각기를 구비한 4구 플라스크에, 2,2－비스(4－히드록시페닐)프로판 246.1 g(1.08 몰), 디페닐카보네이트 237.1 g(1.12 몰)을 넣고, 반응용기를 질소치환한 후, 110℃에서 0.08% 탄산세슘 수용액 0.9 g을 첨가하였다. 220℃까지 승온한 후, 상압에서 40분 반응시켜, 생성된 페놀을 유출시키면서, 80분에 걸쳐 감압도를 13.3 ㎪로 하고, 240℃까지 승온 후, 40분에 걸쳐 감압도를 0.8 ㎪로 하였다. 또한 285℃까지 승온하고, 0.7 ㎪에서 7시간 반응하여, 반응 종료액 250 g을 얻었다. To a 4-neck flask equipped with a thermometer, stirrer, and cooler, 246.1 g (1.08 mol) of 2,2-bis(4-hydroxyphenyl)propane and 237.1 g (1.12 mol) of diphenyl carbonate were added, and the reaction vessel was replaced with nitrogen. After that, 0.9 g of 0.08% cesium carbonate aqueous solution was added at 110°C. After the temperature was raised to 220°C, the reaction was carried out at normal pressure for 40 minutes, while the generated phenol was distilled out, the degree of reduced pressure was 13.3 kPa over 80 minutes, and the temperature was raised to 240°C, and the degree of reduced pressure was 0.8 kPa over 40 minutes. . Moreover, it heated up to 285 degreeC, and it reacted for 7 hours at 0.7 kPa, and obtained the reaction completion liquid 250g.
이어서, 얻어진 반응 종료액 중 150.0 g을 디클로로메탄 530.0 g에 용해시킨 용액을 메탄올 1850 g 중에 적하하여, 목적물을 침전시켰다. 1시간 교반한 후, 침전물을 여과 분별하고, 건조하여, 분말상의 폴리카보네이트를 취득하였다. Next, a solution in which 150.0 g of the obtained reaction termination liquid was dissolved in 530.0 g of dichloromethane was added dropwise to 1850 g of methanol to precipitate the target substance. After stirring for 1 hour, the precipitate was separated by filtration and dried to obtain a powdery polycarbonate.
얻어진 폴리카보네이트의 중량 평균 분자량은 31,240(겔 침투 크로마토그래피), 말단 히드록실 농도는 0.13 mmol／g이었다. The weight average molecular weight of the obtained polycarbonate was 31,240 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.13 mmol/g.
다음으로 온도계, 교반기, 냉각기를 구비한 4구 플라스크에, 얻어진 폴리카보네이트 13.6 g을 넣고, 반응용기를 질소치환한 후, 아크릴산 클로라이드 0.3 g(0.003 몰), 디클로로메탄 47.6 g을, 질소 기류하에서 첨가한 후, 15℃에서 트리에틸아민 0.4 g(0.004 몰)을 첨가하였다. 2시간 교반 후, 메탄올 163 g 중에 반응액을 첨가하여, 목적물을 침전시켰다. 그 후, 침전물을 여과 분별하고, 건조하여, 얻어진 웨트 케이크 14.1 g을 디클로로메탄 47.6 g에 용해시키고, 그 용해액을 메탄올 163 g 중에 첨가하여, 침전시켰다. 그 후, 침전물을 여과 분별하고, 건조하여, 백색 분말상의 화합물 13 g을 취득하였다. Next, into a four-necked flask equipped with a thermometer, stirrer, and cooler, 13.6 g of the obtained polycarbonate was added, and the reaction vessel was replaced with nitrogen, and then 0.3 g (0.003 mol) of acrylic acid chloride and 47.6 g of dichloromethane were added under a nitrogen stream. Then, 0.4 g (0.004 mol) of triethylamine was added at 15°C. After stirring for 2 hours, the reaction solution was added to 163 g of methanol, and the target substance was precipitated. Thereafter, the precipitate was separated by filtration and dried, and 14.1 g of the obtained wet cake was dissolved in 47.6 g of dichloromethane, and the solution was added to 163 g of methanol to precipitate. Then, the precipitate was separated by filtration and dried to obtain 13 g of a white powdery compound.
얻어진 화합물의 1H－NMR의 분석결과로부터, 말단 디아크릴폴리카보네이트인 것을 확인하였다. From the analysis results of 1 H-NMR of the obtained compound, it was confirmed that it was a terminal diacrylic polycarbonate.
말단 디아크릴폴리카보네이트 0.4 g에 대해 시클로헥사논 8.0 g을 사용하였으나 용해되지 않았다. 또한, 시클로헥사논 대신에 디클로로메탄을 사용하고, 말단 디아크릴폴리카보네이트 0.6 g, 다관능 아크릴레이트인 펜타에리스리톨테트라아크릴레이트 2.4 g, 디클로로메탄 3.0 g을 혼합한 혼합물은 백탁 상태로, 투명한 용액을 얻을 수 없었다. 8.0 g of cyclohexanone was used for 0.4 g of terminal diacrylic polycarbonate, but it was not dissolved. In addition, dichloromethane was used in place of cyclohexanone, and a mixture of 0.6 g of terminal diacrylic polycarbonate, 2.4 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 3.0 g of dichloromethane, were mixed in a cloudy state, and a transparent solution was prepared. Couldn't get it.
이상의 결과로부터, 본 발명의 식(1) 및／또는 (2)로 표시되는 말단 (메타)아크릴레이트 폴리카보네이트 올리고머는, 중량 평균 분자량(Mw)을 특정 범위 내의 것으로 함으로써, 유기 용매에 양호한 용해성을 나타내고, 또한, 다관능 아크릴레이트 등과의 상용성이 우수한 것이 명확해졌다. From the above results, the terminal (meth)acrylate polycarbonate oligomer represented by formulas (1) and/or (2) of the present invention has good solubility in an organic solvent by making the weight average molecular weight (Mw) within a specific range. Moreover, it became clear that compatibility with polyfunctional acrylate etc. was excellent.
Claims (1)
(식(1), (2) 중, R1∼R4는 각각 독립적으로 수소원자, 탄소원자수 1∼8의 알킬기, 탄소수 5∼12의 시클로알킬기, 탄소원자수 1∼8의 알콕시기, 또는 탄소원자수 6∼12의 방향족 탄화수소기를 나타내고, R5는 각각 독립적으로 수소원자 또는 메틸기를 나타내며, R6, R7은 각각 독립적으로 수소원자 또는 탄소원자수 1∼14의 알킬기를 나타내고, X는 탄소원자수 2∼4의 알킬렌기를 나타내며, n은 1 이상의 정수이다. 단, R6 및 R7의 탄소원자수의 합계는 14 이하이고, X에 결합해 있는 2개의 산소원자는 X의 동일 탄소원자에는 결합하지 않는다.)A terminal (meth)acrylate polycarbonate oligomer represented by the following formulas (1) and/or (2), wherein the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.
(In formulas (1) and (2), R 1 to R 4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon source. Represents an aromatic hydrocarbon group of 6 to 12 embroidery, R 5 each independently represents a hydrogen atom or a methyl group, R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and X is 2 carbon atoms Represents an alkylene group of ∼4, and n is an integer greater than or equal to 1. However, the total number of carbon atoms of R 6 and R 7 is 14 or less, and the two oxygen atoms bonded to X are not bonded to the same carbon atom of X. I don't.)
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| PCT/JP2019/024236 WO2020008879A1 (en) | 2018-07-05 | 2019-06-19 | (meth)acrylate-terminated polycarbonate oligomer |
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| WO2023145108A1 (en) * | 2022-01-25 | 2023-08-03 | Dic株式会社 | Curable resin, curable resin composition, and cured article |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6155106A (en) * | 1984-08-24 | 1986-03-19 | Tokuyama Soda Co Ltd | Liquid prepolymer |
| JPS6183212A (en) * | 1984-10-01 | 1986-04-26 | Tokuyama Soda Co Ltd | High-refractive index resin |
| JPH03217407A (en) * | 1990-01-23 | 1991-09-25 | Mitsubishi Petrochem Co Ltd | Preparation of high refractive index resin |
| JPH0841044A (en) * | 1994-07-22 | 1996-02-13 | Bayer Ag | Di(meth)acrylate with cyclic carbonate group |
| JPH1081720A (en) * | 1996-09-05 | 1998-03-31 | Nof Corp | Resin composition for casting polymerization and optical material |
| JP2006028418A (en) * | 2004-07-20 | 2006-02-02 | Japan Composite Co Ltd | Radical-curable resin composition |
| JP2010024255A (en) | 2008-07-15 | 2010-02-04 | Nippon Synthetic Chem Ind Co Ltd:The | Active energy ray-curing resin composition and coating agent composition |
| JP2016011365A (en) | 2014-06-30 | 2016-01-21 | アイカ工業株式会社 | Ultraviolet-curable hard coat agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302829A (en) * | 1999-04-23 | 2000-10-31 | Jsr Corp | Liquid curable resin composition and cured substance thereof |
| TWI549986B (en) * | 2011-05-19 | 2016-09-21 | Mitsubishi Gas Chemical Co | A high-flow polycarbonate copolymer, a method for producing a high molecular weight aromatic polycarbonate resin, and an aromatic polycarbonate compound |
| WO2013065755A1 (en) | 2011-11-01 | 2013-05-10 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| JP6155106B2 (en) | 2013-06-14 | 2017-06-28 | セコム株式会社 | Image sensor |
| KR102601255B1 (en) * | 2015-12-08 | 2023-11-09 | 혼슈우 카가쿠고교 가부시키가이샤 | Aromatic polycarbonate oligomer solid |
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- 2019-06-19 WO PCT/JP2019/024236 patent/WO2020008879A1/en active Application Filing
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6155106A (en) * | 1984-08-24 | 1986-03-19 | Tokuyama Soda Co Ltd | Liquid prepolymer |
| JPS6183212A (en) * | 1984-10-01 | 1986-04-26 | Tokuyama Soda Co Ltd | High-refractive index resin |
| JPH03217407A (en) * | 1990-01-23 | 1991-09-25 | Mitsubishi Petrochem Co Ltd | Preparation of high refractive index resin |
| JPH0841044A (en) * | 1994-07-22 | 1996-02-13 | Bayer Ag | Di(meth)acrylate with cyclic carbonate group |
| JPH1081720A (en) * | 1996-09-05 | 1998-03-31 | Nof Corp | Resin composition for casting polymerization and optical material |
| JP2006028418A (en) * | 2004-07-20 | 2006-02-02 | Japan Composite Co Ltd | Radical-curable resin composition |
| JP2010024255A (en) | 2008-07-15 | 2010-02-04 | Nippon Synthetic Chem Ind Co Ltd:The | Active energy ray-curing resin composition and coating agent composition |
| JP2016011365A (en) | 2014-06-30 | 2016-01-21 | アイカ工業株式会社 | Ultraviolet-curable hard coat agent |
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| Publication number | Publication date |
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| TWI794523B (en) | 2023-03-01 |
| TW202006010A (en) | 2020-02-01 |
| CN112424259B (en) | 2022-11-08 |
| JP7253548B2 (en) | 2023-04-06 |
| JPWO2020008879A1 (en) | 2021-07-08 |
| KR102637355B1 (en) | 2024-02-15 |
| CN112424259A (en) | 2021-02-26 |
| WO2020008879A1 (en) | 2020-01-09 |
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