KR101494850B1 - Cage-cleavable siloxane resin having functional group and method for production thereof - Google Patents
Cage-cleavable siloxane resin having functional group and method for production thereof Download PDFInfo
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- KR101494850B1 KR101494850B1 KR1020097017813A KR20097017813A KR101494850B1 KR 101494850 B1 KR101494850 B1 KR 101494850B1 KR 1020097017813 A KR1020097017813 A KR 1020097017813A KR 20097017813 A KR20097017813 A KR 20097017813A KR 101494850 B1 KR101494850 B1 KR 101494850B1
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- South Korea
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- group
- cage
- meth
- reaction
- solvent
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011347 resin Substances 0.000 title claims abstract description 70
- 229920005989 resin Polymers 0.000 title claims abstract description 70
- 125000000524 functional group Chemical group 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- -1 disiloxane compound Chemical class 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 34
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 33
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 28
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 27
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000000466 oxiranyl group Chemical group 0.000 claims abstract description 14
- 238000011067 equilibration Methods 0.000 claims abstract description 13
- 239000002798 polar solvent Substances 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 150000003377 silicon compounds Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003776 cleavage reaction Methods 0.000 description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000007017 scission Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZIFLDVXQTMSDJE-UHFFFAOYSA-N 3-[[dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]silyl]oxy-dimethylsilyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)CCCOC(=O)C(C)=C ZIFLDVXQTMSDJE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical class O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- YQJPWWLJDNCSCN-UHFFFAOYSA-N 1,3-diphenyltetramethyldisiloxane Chemical compound C=1C=CC=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=CC=C1 YQJPWWLJDNCSCN-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AMZNFNXOVYDPBW-UHFFFAOYSA-N 3-[[dimethyl(3-prop-2-enoyloxypropyl)silyl]oxy-dimethylsilyl]propyl prop-2-enoate Chemical compound C=CC(=O)OCCC[Si](C)(C)O[Si](C)(C)CCCOC(=O)C=C AMZNFNXOVYDPBW-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- UDKHNARLWNTSGT-UHFFFAOYSA-N [[dimethyl(2-methylprop-2-enoyloxymethyl)silyl]oxy-dimethylsilyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](C)(C)O[Si](C)(C)COC(=O)C(C)=C UDKHNARLWNTSGT-UHFFFAOYSA-N 0.000 description 1
- BKPKTOIGWIYKJZ-UHFFFAOYSA-N [bis(ethenyl)-methylsilyl]oxy-bis(ethenyl)-methylsilane Chemical compound C=C[Si](C=C)(C)O[Si](C)(C=C)C=C BKPKTOIGWIYKJZ-UHFFFAOYSA-N 0.000 description 1
- VZSZUXBTVQNMOY-UHFFFAOYSA-N [dimethyl(octyl)silyl]oxy-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)O[Si](C)(C)CCCCCCCC VZSZUXBTVQNMOY-UHFFFAOYSA-N 0.000 description 1
- WRFKIQJSBJCNCF-UHFFFAOYSA-N [dimethyl(pentyl)silyl]oxy-dimethyl-pentylsilane Chemical compound CCCCC[Si](C)(C)O[Si](C)(C)CCCCC WRFKIQJSBJCNCF-UHFFFAOYSA-N 0.000 description 1
- KYTGWYJWMAKBPN-UHFFFAOYSA-N [dimethyl(prop-2-enyl)silyl]oxy-dimethyl-prop-2-enylsilane Chemical compound C=CC[Si](C)(C)O[Si](C)(C)CC=C KYTGWYJWMAKBPN-UHFFFAOYSA-N 0.000 description 1
- YIIAFYZYURUBMN-UHFFFAOYSA-N [dimethyl(propyl)silyl]oxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)O[Si](C)(C)CCC YIIAFYZYURUBMN-UHFFFAOYSA-N 0.000 description 1
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- RYBVCZSZPZFJOK-UHFFFAOYSA-N butyl-[butyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound CCCC[Si](C)(C)O[Si](C)(C)CCCC RYBVCZSZPZFJOK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 description 1
- ICYXLXKMZOOGPX-UHFFFAOYSA-N dimethylsilyloxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[SiH](C)O[Si](C)(C)CCCOCC1CO1 ICYXLXKMZOOGPX-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- WILBTFWIBAOWLN-UHFFFAOYSA-N triethyl(triethylsilyloxy)silane Chemical compound CC[Si](CC)(CC)O[Si](CC)(CC)CC WILBTFWIBAOWLN-UHFFFAOYSA-N 0.000 description 1
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- IVZTVZJLMIHPEY-UHFFFAOYSA-N triphenyl(triphenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IVZTVZJLMIHPEY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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Abstract
다른 수지와 상용성이 있고, 분자량 분포 및 분자 구조가 제어된 비닐기, 알킬기, 페닐기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 케이지 개열형 실록산수지 및 이 케이지 개열형 실록산수지를 고수율로 얻는 방법을 제공한다.A cage-cleavable siloxane resin having compatibility with other resins and having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring whose molecular weight distribution and molecular structure are controlled, and a cage- In a high yield.
하기 일반식(1)(1)
[단, R1은 비닐기, 알킬기, 페닐기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기이고, X는 알콕시기, 할로겐원자 또는 히드록실기로부터 선택된 가수분해성 기를 나타낸다.](Wherein R 1 represents a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane group, and X represents a hydrolysable group selected from an alkoxy group, a halogen atom or a hydroxyl group.
로 표현되는 규소화합물의 1종 또는 2종 이상을, 염기성 촉매 존재하, 비극성 용매 또는 극성 용매의 어느 한 쪽 또는 양 쪽을 합친 용매 중에서 가수분해 반응시키는 동시에 일부 축합시키고, 얻어진 중축합물을 또한 비극성 용매 및 염기성 촉매의 존재하에서 재축합시켜, 얻어진 재축합물에 디실록산화합물을 평형화 반응시켜 케이지 개열형 실록산수지를 얻는다.Is subjected to a hydrolysis reaction and a partial condensation in the presence of a basic catalyst in a solvent in which either or both of a non-polar solvent and a polar solvent are combined, and the resulting polycondensate is further subjected to a non-polar Recondensation in the presence of a solvent and a basic catalyst, and a disiloxane compound is subjected to equilibration reaction to the obtained recondensate to obtain a cage-cleavable siloxane resin.
관능기, 케이지 개열형 실록산수지, 디실록산화합물 Functional group, cage-cleavable siloxane resin, disiloxane compound
Description
본 발명은, 케이지 개열형 실록산수지 및 그 제조방법에 관한 것으로서, 상세하게는 규소원자에 비닐기, 알킬기, 페닐기, (메타)아크릴기, 알릴기 또는 옥시란(oxirane) 환으로부터 선택된 1종 또는 2종 이상의 유기 관능기를 가지고, 그 중 적어도 2개는 비닐기, (메타)아크릴기 또는 알릴기로부터 선택된 불포화 이중 결합을 포함하는 반응성 유기 관능기를 가진 케이지 개열형 실록산수지 및 그 제조방법에 관한 것이다.More specifically, the present invention relates to a cage-cleavable siloxane resin and a method for producing the same. More specifically, the present invention relates to a cage-cleavable siloxane resin and a method for producing the same. At least two of which have a reactive organic functional group containing an unsaturated double bond selected from a vinyl group, a (meth) acrylic group or an allyl group, and a process for preparing the cured siloxane resin .
폴리페닐실록산은, 내열성, 전기 절연성 등이 뛰어나기 때문에 코팅재, 실링재, 층간 절연막 그 외에 이용되고 있다. 이 폴리페닐실록산의 제조방법의 일례로서는, 페닐트리클로로실란을 유기 용제 중에서 가수분해하여 페닐트리히드록시실란으로 하여, 상기 가수분해물을 물이 없는 용매 중에서 알칼리성 전이 및 축합 촉매를 사용해 가열하고, 탈수 축중합(縮重合)시켜 케이지형 옥타페닐실록산을 얻는 방법(특허문헌 1), 상기 케이지형 옥타페닐실록산을 분리하고, 다시 알칼리성 전이 및 축합 촉매를 사용해 가열 중합하여 고유 점도가 낮은 페닐실록산 프리 폴리머를 얻는 방법(특허문헌 2), 그것을 또한 알칼리성 전이 및 축중합 촉매를 사용해 가열 중합시켜 페닐실록산 중합체를 제조하는 방법(비특허문헌 1) 등이 알려져 있다.Polyphenylsiloxane is used as a coating material, a sealing material, an interlayer insulating film, and the like because it is excellent in heat resistance, electrical insulation and the like. As an example of the method for producing the polyphenylsiloxane, phenyltrichlorosilane is hydrolyzed in an organic solvent to give phenyltrihydroxysilane, the hydrolyzate is heated in a water-free solvent using an alkaline transition and condensation catalyst, (Patent Document 1). The cage-type octaphenylsiloxane is separated and then heat-polymerized using an alkaline transition and condensation catalyst to obtain a phenylsiloxane prepolymer having a low intrinsic viscosity (Patent Document 2), and a method of producing a phenylsiloxane polymer by heat polymerization using an alkaline transition and polycondensation catalyst (Non-Patent Document 1).
또한 케이지형을 형성하는 실록산수지의 일부의 실록산 결합이 끊어져, 케이지의 일부가 개열된 케이지 개열형 실록산수지의 합성법으로서, 시클로헥실기를 가지는 실록산의 합성법이 Feher,F.J.에 의해 보고되어 있고(비특허문헌 2 참조), 그 이외에도, 예를 들면 페닐기와 비닐기를 가지는 케이지 개열형 실록산수지의 제조방법이 보고되어 있다(특허문헌 3 참조).Further, as a method of synthesizing a cage-cleavable siloxane resin in which a part of the siloxane bond forming the cage type is broken and a part of the cage is cleaved, a method of synthesizing a siloxane having a cyclohexyl group is reported by Feher, FJ Patent Document 2). In addition, a method of producing a cage-cleavable siloxane resin having, for example, a phenyl group and a vinyl group has been reported (see Patent Document 3).
또한 상기 특허문헌 3에서는, 실라놀기를 포함하지 않는 케이지형 폴리페닐실세스퀴옥산의 분자쇄 말단의 SiO 전부 또는 일부에, 반응성 관능기를 가지는 트리오르가노실릴기가 결합한 실리콘화합물을, 유기 용제 중 알칼리성 전이 및 축합 촉매의 존재하에서 가열하고, 평형 반응시켜 반응성 관능기를 가지는 페닐실록산 중합체의 제조방법이 기재되어 있다.In
[특허문헌 1] 일본국 공고특허공보 소40-1598900호[Patent Document 1] Published Japanese Patent Application No. 40-1598900
[특허문헌 2] 일본국 공개특허공보 소50-139900호[Patent Document 2] JP-A-50-139900
[특허문헌 3] 일본국 공개특허공보 평10-251407호[Patent Document 3] Japanese Patent Application Laid-Open No. 10-251407
[비특허문헌 1] J.Polymer Sci. Part C No.1, PP.83-97(1963)[Non-Patent Document 1] J. Polymer Sci. Part C No. 1, pp. 83-97 (1963)
[비특허문헌 2] J.Am. Chem. Soc. 111, 1741-8(1989)[Non-Patent Document 2] J. Am. Chem. Soc. 111, 1741-8 (1989)
상술한 바와 같은 종래의 케이지 개열형 실록산수지의 합성방법은, 긴 반응 시간을 요하고 고수율로 목적물이 얻어지지 않으며, 경화성을 가지는 반응성 관능기의 수가 적기 때문에 충분한 탄성율이나 열선팽창율 등의 물성이 얻어지지 않는다. 한편, 경화성을 가지는 반응성 관능기 1종류만을 모든 규소원자에 가지는 케이지형 실록산은 분자 구조의 대칭성이 좋기 때문에 결정성이 높다. 그 때문에, 다른 수지와의 상용성이 좋지 않아 다른 수지와 혼합하여 물성을 개질한 다양한 성형체를 작성하는 것이 곤란하다.The conventional method of synthesizing a cage-cleavable siloxane resin as described above requires a long reaction time and can not obtain an object at a high yield. Since the number of reactive functional groups having curing property is small, properties such as sufficient elastic modulus and thermal linear expansion coefficient are obtained It does not. On the other hand, the cage siloxane having only one reactive functional group having all of the curable silicon atoms has high crystallinity because of its good symmetry of the molecular structure. For this reason, it is difficult to prepare various molded articles modified in physical properties by mixing with other resins because the compatibility with other resins is poor.
본 발명의 목적은, 종래의 결점을 해소하여, 다른 수지와 상용성이 있고, 분자량 분포 및 분자 구조가 제어된 비닐기, 알킬기, 페닐기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 케이지 개열형 실록산수지를 제공하는 것에 있다. 또한 이러한 케이지 개열형 실록산수지를 고수율로 제조하는 방법을 제공하는 것에 있다.An object of the present invention is to solve the conventional drawbacks and to provide a resin composition which is compatible with other resins and has a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring having a controlled molecular weight distribution and molecular structure Which is a cage-cleavable siloxane resin. And a method for producing such a cage-cleavable siloxane resin at a high yield.
본 발명자들은, 상기 과제를 해결하기 위해 예의 검토를 거듭한 결과, 특정 반응 조건에 의해 이것을 해결할 수 있는 것을 발견하여, 본 발명을 완성하기에 이르렀다.DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, they have found that this can be solved by specific reaction conditions, and have completed the present invention.
즉, 본 발명은, 하기 일반식(2)That is, the present invention provides a compound represented by the following general formula (2)
[단, 반복 단위 m의 구조에서의 R1은 비닐기, 알킬기, 페닐기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기이고, 반복 단위 n의 구조에서의 R1은 비닐기, 알킬기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기이며, (m+n)개의 R1 중의 적어도 2개는 불포화 이중 결합을 가지는 비닐기, (메타)아크릴로일기 또는 알릴기로부터 선택된 반응성 유기 관능기이면서, 반복 단위 n에 있어서 n개의 R1 중 적어도 한 개는 불포화 이중 결합을 가지는 비닐기, (메타)아크릴로일기 또는 알릴기를 가지는 기로부터 선택된 반응성 유기 관능기이며, R2는 메틸기를 나타낸다. m은 1~4의 정수, n은 8~16의 정수이고, m과 n의 합은 10~20이다.]로 표현되는 케이지 개열형 실록산수지이다.R 1 in the structure of the repeating unit m is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 1 in the structure of the repeating unit n is a vinyl group (Meth) acryloyl group, an allyl group or an oxylane group, at least two of (m + n) R 1 s are a vinyl group having an unsaturated double bond, a (meth) acryloyl group or an allyl group And at least one of n R < 1 > in the repeating unit n is a reactive organic functional group selected from a vinyl group having an unsaturated double bond, a (meth) acryloyl group or an allyl group, and R < 2 > Represents a methyl group. m is an integer of 1 to 4, n is an integer of 8 to 16, and the sum of m and n is 10 to 20.) is a cage-cleavable siloxane resin.
또한 본 발명은, 하기 일반식(1)The present invention also provides a compound represented by the following general formula (1)
[단, R1은 비닐기, 알킬기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기이고, X는 알콕시기, 할로겐원자 또는 히드록실기로부터 선택된 가수분해성 기를 나타낸다.]로 표현되는 1종 또는 2종 이상으로서, 적어도 1종의 R1은 불포화 이중 결합을 가지는 비닐기, (메타)아크릴로일기 또는 알릴기인 규소화합물을, 염기성 촉매 존재하, 비극성 용매 또는 극성 용매의 어느 한 쪽 또는 양 쪽을 합친 용매 중에서 가수분해 반응시키는 동시에 일부 축합시키고, 얻어진 중축합물을 또한 비극성 용매 및 염기성 촉매의 존재하에서 재축합시켜, 얻어진 재축합물에 디실록산화합물을 평형화 반응시킴으로써 얻어지는 케이지 개열형 실록산수지이다.(Wherein R 1 represents a vinyl group, an alkyl group, a (meth) acryloyl group, an allyl group, or an oxirane group, and X represents a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group And at least one kind of R 1 is a vinyl group, a (meth) acryloyl group or an allyl group, which is an unsaturated double bond, in the presence of a basic catalyst in either a nonpolar solvent or a polar solvent Obtained by subjecting a condensate to a hydrolysis reaction and a partial condensation in a solvent in which a non-polar solvent and a basic catalyst are mixed in a solvent, and the resultant polycondensate is further subjected to a recondensation in the presence of a non-polar solvent and a basic catalyst, Siloxane resin.
또한 본 발명은, 하기 일반식(1)The present invention also provides a compound represented by the following general formula (1)
[단, R1은 비닐기, 알킬기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기이고, X는 알콕시기, 할로겐원자 또는 히드록실기로부터 선택된 가수분해성 기를 나타낸다.]로 표현되는 1종 또는 2종 이상으로서, 적어도 1종의 R1은 불포화 이중 결합을 가지는 비닐기, (메타)아크릴로일기 또는 알릴기인 규소화합물을, 염기성 촉매 존재하, 비극성 용매 또는 극성 용매의 어느 한 쪽 또는 양 쪽을 합친 용매 중에서 가수분해 반응시키는 동시에 일부 축합시키고, 얻어진 중축합물을 또한 비극성 용매 및 염기성 촉매의 존재하에서 재축합시켜, 얻어진 재축합물에 디실록산화합물을 평형화 반응시키는 것을 특징으로 하는 케이지 개열형 실록산수지의 제조방법이다.(Wherein R 1 represents a vinyl group, an alkyl group, a (meth) acryloyl group, an allyl group, or an oxirane group, and X represents a hydrolyzable group selected from an alkoxy group, a halogen atom or a hydroxyl group And at least one kind of R 1 is a vinyl group, a (meth) acryloyl group or an allyl group, which is an unsaturated double bond, in the presence of a basic catalyst in either a nonpolar solvent or a polar solvent Or a condensation reaction in the presence of a non-polar solvent and a basic catalyst, and subjecting the resultant polycondensate to a recondensation in the presence of a non-polar solvent and a basic catalyst, and subjecting the obtained recondensate to equilibration reaction with the recondensate Cage-cleavable siloxane resin.
본 발명에서의 케이지 개열형 실록산수지의 구조식의 예를 하기 식(4)~(10)에 나타낸다. 여기서, 구조식(4)은 일반식(2)에 있어서 m=2 및 n=8의 경우이고, 이하 마찬가지로 (5)는 m=3, n=9, (6)은 m=2, n=10, (7)은 m=3, n=11, (8)은 m=2, n=12, (9)는 m=3, n=13, (10)은 m=2, n=14이다. 또한 본 발명의 케이지 개열형 실록산수지는 이들 이외의 m, n 수를 취하는 것도 있어, 이에 한정되지 않는다. 또한 구조식(4)~(10)에서의 R1 및 R2는 일반식(2)의 경우와 같다.Examples of structural formulas of the cage-cleavable siloxane resin in the present invention are shown by the following formulas (4) to (10). M = 2 and n = 8 in the formula (4), m = 3 and n = 9 in the formula (5) (7) are m = 3, n = 11, (8) are m = 2, n = 12, m = 3 and n = 13 and m = 2 and n = 14. Further, the cage-cleavable siloxane resin of the present invention may take other numbers m and n than those, and the present invention is not limited thereto. R 1 and R 2 in the structural formulas (4) to (10) are the same as those in the general formula (2).
본 발명의 케이지 개열형 실록산수지의 제조방법에서는, 우선 일반식(1)로 표현되는 규소화합물을, 염기성 촉매 존재하, 비극성 용매 또는 극성 용매의 어느 한 쪽 또는 양 쪽을 합친 용매 중에서 가수분해 반응을 행한다. 일반식(1) 중 R1은 비닐기, 알킬기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기로부터 선택되는 유기기이고, 경화성을 부여하기 위해 불포화 이중 결합을 가지는 기를 포함한다.In the method for producing a cage-cleavable siloxane resin of the present invention, first, the silicon compound represented by the general formula (1) is hydrolyzed in the presence of a basic catalyst in a solvent containing a nonpolar solvent or a polar solvent, . In the general formula (1), R 1 is an organic group selected from a group having a vinyl group, an alkyl group, a (meth) acryloyl group, an allyl group or an oxirane group, and includes a group having an unsaturated double bond for imparting curability .
일반식(1)에 있어서, X는 가수분해성 기이고, 구체적으로는 알콕시기, 할로겐원자 또는 히드록실기를 들 수 있는데, 알콕실기인 것이 바람직하다. 알콕시기로서는 메톡시기, 에톡시기, n- 및 i-프로폭시기, n-, i- 및 t-부톡시기 등을 들 수 있다. 이 중 반응성이 높은 메톡시기인 것이 바람직하다.In the general formula (1), X is a hydrolyzable group, specifically, an alkoxy group, a halogen atom or a hydroxyl group, preferably an alkoxyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, n- and i-propoxy groups, n-, i- and t-butoxy groups and the like. Of these, a methoxy group having a high reactivity is preferable.
일반식(1)로 표현되는 규소화합물에 대하여, 바람직한 화합물의 구체예를 나타내면, 페닐트리메톡시실란, 페닐트리에톡시실란, 메틸트리메톡시실란, 메틸트리에톡시실란, 에틸트리메톡시실란, 에틸트리에톡시실란, n-프로필트리메톡시실란, n-프로필트리에톡시실란, 부틸트리메톡시실란, 부틸트리에톡시실란, 펜틸트리메톡시실란, 펜틸트리에톡시실란, 옥틸트리메톡시실란, 옥틸트리에톡시실란, 메타크릴옥시메틸트리메톡시실란, 메타크릴옥시메틸트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-아크릴옥시프로필트리메톡시실란, 3-아크릴옥시프로필트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 2-(3,4-에폭시시클로헥실에틸)트리메톡시실란, 알릴트리메톡시실란, 알릴트리에톡시실란, p-스티릴트리에톡시실란, p-스티릴트리메톡시실란, 비닐트리메톡시실란, 및 비닐트리에톡시실란 등을 들 수 있다. 그 중에서도, 원료의 입수가 용이한 페닐트리메톡시실란, 메틸트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 및 비닐트리메톡시실란이 보다 바람직하다.Specific examples of preferred compounds for the silicon compound represented by the general formula (1) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, octyltrimethyl 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, -Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclo Hexylethyl) trimethoxysilane, allyltrimethoxysilane Sisilran, it is in the allyl triethoxysilane, p- styryl triethoxysilane, p- styryl trimethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, and the and the like silane. Among them, phenyltrimethoxysilane, methyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane, which are easily available from raw materials, More preferable.
상기 가수분해 반응에 사용되는 염기성 촉매로서는, 수산화칼륨, 수산화나트륨, 수산화세슘 등의 알칼리 금속 수산화물 외에 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라부틸암모늄히드록시드, 벤질트리메틸암모늄히드록시드, 벤질트리에틸암모늄히드록시드 등의 수산화암모늄 염이 예시된다. 이 중에서도, 촉매 활성이 높은 점에서 테트라메틸암모늄히드록시드가 바람직하게 사용된다. 염기성 촉매는 통상 수용액으로서 사용된다.Examples of the basic catalyst used in the hydrolysis reaction include, in addition to alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide And ammonium hydroxide salts such as benzyltriethylammonium hydroxide, and the like. Of these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity. The basic catalyst is usually used as an aqueous solution.
가수분해 반응 조건에 대해서는, 반응 온도는 0~60℃가 바람직하고, 20~40℃가 보다 바람직하다. 반응 온도가 0℃보다 낮으면, 반응 속도가 늦어져 가수분해성 기가 미반응의 상태로 잔존해 버려 반응 시간을 많이 소비하는 결과가 된다. 한편, 60℃보다 높으면, 반응 속도가 지나치게 빠르기 때문에 복잡한 축합 반응이 진행되어 결과적으로 가수분해 생성물의 고분자량화가 촉진된다. 또한 반응 시간은 2시간 이상이 바람직하다. 반응 시간이 2시간에 미치지 못하면, 가수분해 반응이 충분히 진행되지 않아 가수분해성 기가 미반응의 상태로 잔존해 버리는 상태가 된다.As for the hydrolysis reaction conditions, the reaction temperature is preferably 0 to 60 ° C, more preferably 20 to 40 ° C. If the reaction temperature is lower than 0 ° C, the reaction rate is slowed, and the hydrolyzable group remains in an unreacted state, resulting in a large reaction time. On the other hand, if the reaction temperature is higher than 60 ° C, the reaction rate is excessively high, so that a complicated condensation reaction proceeds, thereby promoting the high molecular weight of the hydrolysis product. The reaction time is preferably 2 hours or more. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group remains in an unreacted state.
가수분해 반응은 물의 존재가 필수인데, 이것은 염기성 촉매의 수용액으로부터 공급할 수도 있고, 별도의 물로서 첨가해도 된다. 물의 양은 가수분해성 기를 가수분해하기에 충분한 양 이상, 바람직하게는 이론량의 1.0~1.5배량인 것이 좋다. 또한 가수분해시에는 비극성 용매 또는 극성 용매 중의 한 개 혹은 양 쪽 합쳐 사용한다. 바람직하게는 양 쪽 사용하거나, 극성 용매만 사용하는 것이 좋다. 극성 용매로서는 메탄올, 에탄올, 2-프로판올 등의 알코올류, 혹은 다른 극성 용매를 사용할 수 있다. 바람직하게는, 물과 용해성이 있는 탄소수 1~6인 저급 알코올류이고, 2-프로판올을 사용하는 것이 보다 바람직하다. 비극성 용매만을 사용하면 반응계가 균일해지지 않아 반응 중 고분자체가 석출하기 쉽다.The hydrolysis reaction requires the presence of water, which may be supplied from an aqueous solution of the basic catalyst or may be added as separate water. The amount of water is preferably at least an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. In the hydrolysis, one of a nonpolar solvent and a polar solvent or both of them are used in combination. Preferably, both of them are used or only a polar solvent is used. As the polar solvent, alcohols such as methanol, ethanol, 2-propanol, or other polar solvents can be used. Preferably, water-soluble lower alcohols having 1 to 6 carbon atoms are used, and 2-propanol is more preferably used. If only a non-polar solvent is used, the reaction system is not uniform, and the polymer body is likely to precipitate during the reaction.
가수분해 반응 종료 후는, 반응 용액을 약산성 용액으로 중화하여 중성 혹은 산성에 가깝게 한 후 물 또는 물 함유 반응 용매를 분리한다. 물 또는 물 함유 반응 용매의 분리는, 이 용액을 식염수 등으로 세정해 수분이나 그 외의 불순물을 충분히 제거하고, 그 후 무수 황산마그네슘 등의 건조제로 건조시키는 등의 수단을 채용할 수 있다. 극성 용매를 사용한 경우는, 감압 증발 등의 수단을 채용할 수 있고, 극성 용매를 제거한 후 비극성 용매를 첨가해 중축합물을 용해시키고 상기와 같이 세정, 건조를 행한다. 약산성 용액에 대해서는, 황산 희석 용액, 염산 희석 용액, 구연산 용액, 아세트산, 염화 암모늄 수용액, 사과산 용액, 인산 용액, 옥살산 용액 등이 사용된다. 비극성 용매는, 증발 등의 수단으로 분리하면 가수분해 반응 생성물을 회수할 수 있지만, 비극성 용매가 다음 반응에서 사용하는 비극성 용매로서 사용 가능하면 이것을 분리할 필요는 없다.After completion of the hydrolysis reaction, neutralize the reaction solution with a slightly acidic solution to bring it closer to neutral or acidic, and then separate the reaction solvent containing water or water. Separation of water or a reaction solvent containing water can be carried out by washing the solution with a saline solution or the like to sufficiently remove water and other impurities, and then drying with a desiccant such as anhydrous magnesium sulfate. When a polar solvent is used, means such as evaporation under reduced pressure can be employed. After the polar solvent is removed, a non-polar solvent is added to dissolve the polycondensate, followed by washing and drying. For the weakly acidic solution, a dilute solution of sulfuric acid, diluted hydrochloric acid solution, citric acid solution, acetic acid, ammonium chloride solution, malic acid solution, phosphoric acid solution, oxalic acid solution and the like are used. The nonpolar solvent can be recovered by separation by means of evaporation or the like, but if the nonpolar solvent can be used as the nonpolar solvent used in the next reaction, it is not necessary to separate it.
본 발명의 가수분해 반응에서는 가수분해와 함께 가수분해물의 축합 반응이 발생한다. 가수분해물의 축합 반응이 수반하는 중축합물은, 통상 수평균분자량이 500~7000인 무색의 점성 액체가 된다. 중축합물은, 반응 조건에 따라 다른데 수평균분자량이 500~3000인 수지(또는 올리고머)가 되고, 일반식(1)로 표현되는 가수분해성 기 X의 대부분, 바람직하게는 거의 전부가 OH기로 치환되고, 또한 그 OH기의 대부분, 바람직하게는 95%이상이 축합되어 있다.In the hydrolysis reaction of the present invention, a condensation reaction of the hydrolyzate occurs together with hydrolysis. The polycondensate accompanied by the condensation reaction of the hydrolyzate generally becomes a colorless viscous liquid having a number average molecular weight of 500 to 7000. The polycondensate is a resin (or oligomer) having a number average molecular weight of 500 to 3000, which varies depending on the reaction conditions. Most, preferably almost all of the hydrolyzable groups X represented by the general formula (1) are substituted with OH groups , And most of the OH groups, preferably 95% or more, are condensed.
중축합물의 구조에 대해서는, 복수 종의 케이지형, 사다리형, 랜덤형의 실록산으로서, 케이지형 구조를 취하고 있는 화합물에 대해서도 완전한 케이지형 구조의 비율은 적고, 케이지의 일부가 열려 있는 불완전한 케이지형의 구조가 주(主)가 되고 있다. 이 중축합물을 또한 비극성 용매 및 염기성 촉매의 존재하에서 가열하여, 실록산 결합을 축합(재축합이라 칭함)시킴으로써 재축합물(케이지형 구조의 실록산)을 선택적으로 제조한다.Regarding the structure of the polycondensate, a plurality of kinds of cage-type, ladder-type, and random-type siloxanes, even in the case of a compound having a cage-type structure, the ratio of the complete cage- The structure is becoming the master. The polycondensate is further heated in the presence of a non-polar solvent and a basic catalyst to selectively condense a siloxane bond (referred to as recondensation) to obtain a recondensate (siloxane having a cage structure).
재축합물을 얻을 때에는, 물 또는 물 함유 반응 용매를 분리한 후 비극성 용매 및 염기성 촉매의 존재하에 재축합 반응을 행한다. 재축합 반응의 반응 조건에 대해서는, 반응 온도는 90~200℃의 범위가 바람직하고, 100~140℃가 보다 바람직하다. 반응 온도가 지나치게 낮으면, 재축합 반응을 시키기 위해 충분한 드라이빙 포스가 얻어지지 않아 반응이 진행되지 않는다. 반응 온도가 지나치게 높으면, 반응성 유기 관능기가 자기 중합 반응을 일으킬 가능성이 있으므로, 반응 온도를 억제하거나, 중합 금지제 등을 첨가할 필요가 있다. 반응 시간은 2~12시간이 바람직하다. 비극성 용매의 사용량은 가수분해 반응 생성물을 용해하기에 충분한 양인 것이 좋고, 염기성 촉매의 사용량은 재축합물에 대하여 0.1~5wt%의 범위이다. 보다 바람직하게는 0.5~2.Owt%의 범위이다.When a recondensate is obtained, a water or a water-containing reaction solvent is separated, and a recondensation reaction is carried out in the presence of a non-polar solvent and a basic catalyst. Regarding the reaction conditions of the recondensation reaction, the reaction temperature is preferably in the range of 90 to 200 캜, more preferably 100 to 140 캜. If the reaction temperature is too low, a sufficient driving force can not be obtained for carrying out the recondensation reaction, and the reaction does not proceed. If the reaction temperature is too high, there is a possibility that the reactive organic functional group may cause a self-polymerization reaction, so it is necessary to suppress the reaction temperature or to add a polymerization inhibitor or the like. The reaction time is preferably 2 to 12 hours. The amount of the nonpolar solvent is preferably sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst to be used is in the range of 0.1 to 5 wt% with respect to the recondensate. And more preferably in the range of 0.5 to 2.0 wt%.
비극성 용매로서는, 물과 용해성이 없거나 또는 거의 없는 것이면 되는데, 탄화수소계 용매가 바람직하다. 탄화수소계 용매로서는 톨루엔, 벤젠, 크실렌 등의 비점이 낮은 비극성 용매를 들 수 있고, 그 중에서도 톨루엔을 사용하는 것이 바람직하다. 한편, 염기성 촉매로서는, 가수분해 반응에 사용되는 염기성 촉매를 사용할 수 있고, 수산화칼륨, 수산화나트륨, 수산화세슘 등의 알칼리 금속 수산화물, 혹은 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라부틸암모늄히드록시드, 벤질트리메틸암모늄히드록시드, 벤질트리에틸암모늄히드록시드 등의 수산화암모늄 염을 들 수 있는데, 테트라알킬암모늄 등의 비극성 용매에 가용성인 촉매가 바람직하다. 또한 일반식(1)의 규소화합물을 염기성 촉매 존재하에서 가수분해 반응시킬 때에 비극성 용매를 사용하는 경우, 상기에서 예시한 바와 같은 것을 사용할 수 있다. 가수분해 반응에서 사용하는 비극성 용매와 재축합물을 얻을 때에 사용하는 비극성 용매는 서로 같은 것을 사용해도 되고, 다른 것을 사용해도 되는데, 합성 순서 등을 간편하게 하기 위해 바람직하게는 서로 같은 것을 사용하는 것이 좋다.The nonpolar solvent may be any one which has little or no solubility in water, and a hydrocarbon solvent is preferred. Examples of the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, and xylene. Of these, toluene is preferably used. On the other hand, as the basic catalyst, a basic catalyst used for the hydrolysis reaction can be used, and an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, cesium hydroxide, or the like, or an alkali metal hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, Ammonium hydroxide such as ammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide, and a catalyst that is soluble in a non-polar solvent such as tetraalkylammonium is preferable. When a non-polar solvent is used for the hydrolysis reaction of the silicon compound of the general formula (1) in the presence of a basic catalyst, those exemplified above can be used. The nonpolar solvent used in the hydrolysis reaction and the nonpolar solvent used in obtaining the recondensate may be the same or different, but it is preferable to use the same solvent to simplify the synthesis procedure and the like .
또한 재축합에 사용하는 가수분해 생성물은 물 세정, 탈수하여 농축한 것을 사용하는 것이 바람직한데, 물 세정, 탈수를 행하지 않아도 사용할 수 있다. 이 반응시, 물은 존재해도 되는데, 적극적으로 첨가할 필요는 없고, 염기성 촉매 용액으로부터 반입되는 수분 정도로 머무르는 것이 좋다. 또한 중축합물의 가수분해가 충분히 행해지지 않고 있는 경우는, 잔존하는 가수분해성 기를 가수분해하는데 필요한 이론량 이상의 수분이 필요하다. 재축합 반응 후는 촉매를 물 세정하여 제거해 농축하여 재축합물이 얻어진다.The hydrolysis product used for the recondensation is preferably water-washed, dehydrated and concentrated, and can be used without washing with water or dehydration. In this reaction, water may be present, but it is not necessary to actively add it, and it is preferable to stay in the moisture to be carried in from the basic catalyst solution. Further, when the hydrolysis of the polycondensate is not sufficiently carried out, it is necessary to use water at least the theoretical amount required for hydrolyzing the remaining hydrolyzable group. After the re-condensation reaction, the catalyst is washed with water, removed and concentrated to obtain a recondensate.
이어서, 상기에서 얻어진 재축합물에 디실록산화합물을 부가시킴으로써 케이지 개열형 실록산수지를 얻을 수 있다. 이 디실록산화합물에 대하여, 구체적으로는 하기 일반식(3)으로 나타낼 수 있다. 또한 재축합물에 디실록산화합물을 부가시킬 때의 반응에 대해서는 톨루엔, 벤젠, 크실렌 등의 비극성 용매, 및 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라부틸암모늄히드록시드 등의 염기성 촉매의 존재하에서 행하는 것이 좋다.Then, a cis-cleaved siloxane resin can be obtained by adding a disiloxane compound to the recondensate obtained above. The disiloxane compound can be specifically represented by the following general formula (3). The reaction for adding the disiloxane compound to the recondensate may be carried out in the presence of a nonpolar solvent such as toluene, benzene or xylene, or a basic solvent such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide It is preferable to carry out the reaction in the presence of a catalyst.
(단, R1은 비닐기, 알킬기, 페닐기, (메타)아크릴로일기, 알릴기 또는 옥시란 환을 가지는 기로부터 선택되는 1종 또는 2종의 기이고, R2는 메틸기를 나타낸다.)(Wherein R 1 is one or two groups selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane group, and R 2 represents a methyl group.
상기한 재축합물과 일반식(3)으로 표현되는 디실록산화합물 사이의 염기 촉매하에서의 부가 반응은 평형화 반응이고, 산소원자가 3/2개 결합한 규소원자 유닛(T 단위)으로 구성되는 재축합물의 개열, 혹은 재축합물 단독에 의한 고분자량화의 경쟁 반응이기 때문에 전자(前者)(재축합물의 개열)를 가능한한 우선적으로 행할 필요가 있다. 또한 본 발명에서의 반응은 기본적으로 평형 반응이기 때문에, 목적물의 말단에 반응성 관능기를 가지는 케이지 개열형 실록산의 수평균분자량 Mn, 수율, 및 생성 속도는 반응 온도, 반응 시간, 양 원료의 첨가량 비, 알칼리 촉매량 등에 의해 저절로 결정되기 때문에 이하에 기술한 조건하에서 행하는 것이 바람직하다.The addition reaction of the above-mentioned recondensate and the disiloxane compound represented by the general formula (3) under the base catalyst is an equilibrium reaction, and the recrystallization reaction of the recondensate composed of the silicon atom unit (T unit) bonded with 3/2 oxygen atoms , Or the competing reaction of high molecular weight by the recondensate alone, it is necessary to perform the former (cleavage of the recondensate) as early as possible. Since the reaction in the present invention is basically an equilibrium reaction, the number-average molecular weight Mn, yield, and production rate of the cage-cleavable siloxane having a reactive functional group at the end of the object are determined by the reaction temperature, reaction time, The amount of the alkali catalyst, and the like, it is preferable to carry out the reaction under the conditions described below.
즉, 상기에서 얻어진 재축합물은 비극성 용매 및 염기성 촉매의 존재하에 일반식(3)으로 나타내는 디실록산화합물을 부가시키는 것이 좋다. 반응 조건에 대해서는, 반응 온도는 90~200℃의 범위가 바람직하고, 100~140℃가 보다 바람직하다. 그러나 일반식(3)으로 표현되는 디실록산화합물의 비점이 낮은 것에 관해서는 반응 온도가 비점 이상에 달하여 반응계 외로 증발할 가능성이 있으므로, 그 경우에는 비점 이하에서 장시간 반응시키는 것이 좋다. 염기성 조건하, 재축합물의 케이지를 형성하는 실록산 결합은 절단과 결합의 평형상태에 있는데, 디실록산화합물이 존재하면, 절단된 부분이 디실록산화합물과 반응하기 때문에 케이지의 일부분이 개열된 상태로 안정되어 케이지 개열형 실록산수지가 얻어진다. 여기서 말하는 케이지 개열형 실록산이란, 케이지 구조를 형성하고 있는 실록산 결합 중 적어도 한 개가 끊어짐으로써 불완전한 케이지 구조를 형성한 실록산 분자 구조를 나타낸다. 또한 반응 시간은 1~5시간이 바람직하다.That is, it is preferable to add the disiloxane compound represented by the general formula (3) in the presence of the non-polar solvent and the basic catalyst. Regarding the reaction conditions, the reaction temperature is preferably in the range of 90 to 200 ° C, more preferably 100 to 140 ° C. However, with respect to the low boiling point of the disiloxane compound represented by the general formula (3), since the reaction temperature reaches the boiling point and may evaporate outside the reaction system, in this case, it is preferable to carry out the reaction for a long time at the boiling point or lower. Under basic conditions, the siloxane bond forming the cage of the recondensate is in equilibrium with the cleavage and binding. When the disiloxane compound is present, the cleaved portion reacts with the disiloxane compound, so that a portion of the cage is stable Whereby a cage-cleavable siloxane resin is obtained. The term "cage cleaved siloxane" as used herein refers to a siloxane molecular structure in which an incomplete cage structure is formed by breaking of at least one siloxane bond forming a cage structure. The reaction time is preferably 1 to 5 hours.
재축합물과 디실록산화합물의 평형화 반응에서 비극성 용매를 사용하는 경우, 비극성 용매의 사용량은 재축합물을 용해하는데 충분한 양인 것이 좋다. 한편, 재축합물과 디실록산화합물의 반응 비율에 대해서는, 재축합물의 T 단위 10개에 상당하는 [R1SiO1.5]10으로 표현되는 구조 단위 1몰에 대하여, 디실록산화합물을 0.5~4.0몰, 바람직하게는 1.0~2.0몰이 되도록 가수분해 부가시키는 것이 좋다. 디실록산화합물이 이 범위보다 적으면 반응이 진행되지 않고, 반대로 많으면 미반응물이 생성물의 물성에 악영향을 끼칠 우려가 있어 바람직하지 않다. 또한 예를 들면 헥사메틸디실록산, 1,3-디비닐-1,1,3,3-테트라메틸디실록산 등과 같이 휘발성이 높은 디실록산화합물을 사용한 경우에는, 반응 중에 휘산(揮散)하는 양도 고려하여 첨가량을 많게 설정해도 지장 없다. 또한 여기서 사용하는 비극성 용매의 예로서는, 재축합물을 얻을 때에 사용하는 것과 같은 것을 예시할 수 있으며, 재축합물을 얻을 때에 사용하는 것과 같아도 되고, 다른 것을 사용해도 된다.When a non-polar solvent is used in the equilibration reaction between the recondensate and the disiloxane compound, the amount of the non-polar solvent is preferably sufficient to dissolve the recondensate. On the other hand, as for the reaction ratio of the recondensate and the disiloxane compound, the disiloxane compound is added in an amount of 0.5 to 4.0 moles per mole of the structural unit represented by [R 1 SiO 1.5 ] 10 corresponding to 10 T units of the recondensate , Preferably 1.0 to 2.0 mols, per mol of the water-soluble polymer. When the amount of the disiloxane compound is less than this range, the reaction does not proceed, and when the amount is too large, unreacted materials may adversely affect the physical properties of the product. Further, when a highly volatile disiloxane compound such as, for example, hexamethyldisiloxane or 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is used, the amount of volatilization during the reaction is also considered So that the addition amount can be set to a large value. Examples of the nonpolar solvent to be used herein include the same ones as those used for obtaining the recondensate, and they may be the same as those used for obtaining the recondensate, and others may be used.
또한 재축합물과 디실록산화합물의 평형화 반응에서 염기성 촉매를 사용하는 경우, 염기성 촉매의 사용량에 대해서는, [R1SiO1.5]10으로 표현되는 재축합물의 구조 단위 1몰에 대하여, 염기성 촉매를 0.05~0.15몰, 바람직하게는 0.06~0.1몰이 되도록 첨가하는 것이 좋다.When the basic catalyst is used in the equilibration reaction between the recondensate and the disiloxane compound, the basic catalyst is used in an amount of 0.05 to 5.0 moles per mole of the structural unit of the recondensate represented by [R 1 SiO 1.5 ] 10 , To 0.15 mol, preferably 0.06 to 0.1 mol, per mol of the compound
일반식(3)으로 표현되는 디실록산화합물에 대하여 바람직한 화합물의 구체예를 나타내면, 1,3-디페닐-1,1,3,3-테트라메틸디실록산, 헥사메틸디실록산, 헥사에틸디실록산, 헥사페닐디실록산, 펜타메틸디실록산, 1,1,3,3-테트라메틸디실록산, 1,1,3,3-테트라비닐디메틸디실록산, 1,3-디에틸-1,1,3,3-테트라메틸디실록산, 1,3-디n-프로필-1,1,3,3-테트라메틸디실록산, 1,3-디부틸-1,1,3,3-테트라메틸디실록산, 1,3-디펜틸-1,1,3,3-테트라메틸디실록산, 1,3-디옥틸-1,1,3,3-테트라메틸디실록산, 1,3-디메타크릴옥시메틸-1,1,3,3-테트라메틸디실록산, 1,3-디(3-메타크릴옥시프로필)-1,1,3,3-테트라메틸디실록산, 1,3-디아크릴옥시메틸-1,1,3,3-테트라메틸디실록산, 1,3-디(3-아크릴옥시프로필)-1,1,3,3-테트라메틸디실록산, 1,3-디(3-글리시독시프로필)-1,1,3,3-테트라메틸디실록산, 비스[2-(3,4-에폭시시클로헥실)에틸]-테트라메틸디실록산, 1,3-디알릴-1,1,3,3-테트라메틸디실록산, 1,2-디p-스티릴-1,1,3,3-테트라메틸디실록산, 및 1,3-디비닐-1,1,3,3-테트라메틸디실록산 등을 들 수 있다.Specific examples of preferred compounds for the disiloxane compound represented by the general formula (3) include 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, hexaethyldisiloxane , Hexaphenyldisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, 1,3-diethyl-1,1,3 Tetramethyldisiloxane, 1,3-di-n-propyl-1,1,3,3-tetramethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, 1,3-dipentyl-1,1,3,3-tetramethyldisiloxane, 1,3-dioctyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethacryloxymethyl- 1,1,3,3-tetramethyldisiloxane, 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-diacryloxymethyl- , 1,3,3-tetramethyldisiloxane, 1,3-di (3-acryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-di (3-glycidoxypropyl) ) -1,1,3,3-tetramethyldisiloxane, bis [2- (3,4-epoxy Hexyl) ethyl] -tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,2-di-p-styryl-1,1,3,3-tetra Methyldisiloxane, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
본 발명에 의해 얻어지는 케이지 개열형 실록산수지는, 일반식(2)의 m이 1~4, n이 8~16이고, m과 n의 합이 10~20으로 나타나는 구조식(4)~(10)으로 표현되는 화합물의 혼합물로서 얻어지는 경우가 많다. 또한 얻어지는 케이지 개열형 실록산수지의 수평균분자량 Mn은 통상 600~10000의 범위이다. 또한, 얻어지는 케이지 개열형 실록산수지는, GPC 차트에서의 최대 면적을 가지는 피크가 차지하는 비율이 50% 이상이고, 분자량 분산도(Mw/Mn)가 1.0~3.5이다.The cage-cleavable siloxane resin obtained by the present invention has the structural formulas (4) to (10) in which m in the general formula (2) is 1 to 4, n is 8 to 16, and the sum of m and n is 10 to 20, In many cases. The number-average molecular weight Mn of the obtained cage-cleavable siloxane resin is usually in the range of 600 to 10,000. The obtained cage-cleavable siloxane resin has a peak occupying 50% or more of the peak having the maximum area in the GPC chart and a molecular weight dispersion (Mw / Mn) of 1.0 to 3.5.
<발명의 효과>EFFECTS OF THE INVENTION [
본 발명의 케이지 개열형 실록산수지의 제조방법을 사용하면, 분자량 분산도가 낮은 구조 제어된 케이지 개열형 실록산수지를 고수율로 제조할 수 있다. 얻어진 케이지 개열형 실록산수지는 분자 구조의 대칭성이 낮고 저점도이며, 반응성 관능기를 가지는 실록산 올리고머와 임의로 배합할 수 있는 상용성을 가지며, 경화성 수지 조성물의 원료로서 널리 사용할 수 있다. 또한 케이지 구조와 유사한 구조의 실록산이기 때문에, 본 발명의 케이지 개열형 실록산수지를 포함하는 경화성 수지 조성물을 경화시켜 얻은 성형체에는 무기 유리와 같은 강도, 투명성, 내열성, 및 치수 안정성을 구비하면서, 플라스틱과 같은 고인성(高靭性), 양호한 가공성이 부여되어, 예를 들면, 렌즈, 광 디스크, 광 파이버 및 플랫 패널 디스플레이 기판 등의 광학 용도나, 각종 수송 기계나 주택 등의 창재(窓材) 등에 적용 가능하고, 또한 경량성이나 고충격 강도 등이 요구되는 각종의 투명 부재에도 사용할 수 있어 이익, 임펙트 모두 크다.By using the process for producing a cage-cleavable siloxane resin of the present invention, a structure-controlled cage-cleavable siloxane resin having a low molecular weight dispersion degree can be produced at a high yield. The cage-cleavable siloxane resin obtained has low molecular structure symmetry and low viscosity, has compatibility with a siloxane oligomer having reactive functional groups and can be widely used as a raw material for a curable resin composition. In addition, since the siloxane has a structure similar to that of the cage structure, the molded article obtained by curing the curable resin composition containing the cage-cleavable siloxane resin of the present invention is excellent in strength, transparency, heat resistance and dimensional stability, And is applied to optical applications such as lenses, optical disks, optical fibers and flat panel display substrates, and window materials such as various transportation machines and houses. And it can be used for various transparent members requiring light weight and high impact strength, so that both profit and impact are great.
도 1은 R1이 CH2=CH-인 재축합물의 GPC 차트이다.1 is a GPC chart of a re-condensation product wherein R 1 is CH 2 = CH-.
도 2는 R1이 CH2=CH-, R2가 CH3-인 케이지 개열형 실록산수지 혼합물의 GPC 차트이다.2 is a GPC chart of a cage-cleavable siloxane resin mixture in which R 1 is CH 2 = CH- and R 2 is CH 3 -.
도 3은 R1이 CH2=CH-, R2가 CH3-인 케이지 개열형 실록산수지 혼합물의 MS 스펙트럼이다.FIG. 3 is an MS spectrum of a cage-cleavable siloxane resin mixture in which R 1 is CH 2 = CH- and R 2 is CH 3 -.
도 4는 R1이 (CH3-:CH2=CH-=5:5)인 재축합물의 GPC 차트이다.4 is a GPC chart of a recondensate wherein R 1 is (CH 3 -: CH 2 = CH- = 5: 5).
도 5는 R1이 (CH3-:CH2=CH-=5:7), R2가 CH3-인 케이지 개열형 실록산수지의 GPC 차트이다.5 is a GPC chart of a cage-cleavable siloxane resin wherein R 1 is (CH 3 -: CH 2 = CH- = 5: 7) and R 2 is CH 3 -.
도 6은 R1이 (CH3-:CH2=CH-=2:10), R2가 CH3-인 케이지 개열형 실록산수지 혼합물의 GPC 차트이다.6 is a GPC chart of a cage-cleavable siloxane resin mixture wherein R 1 is (CH 3 -:
도 7은 R1 및 R2가 도면 중에 나타낸 바와 같은 경우의 케이지 개열형 실록산수지 혼합물의 GPC 차트이다.7 is a GPC chart of a cage-cleavable siloxane resin mixture when R 1 and R 2 are as shown in the figure.
도 8은 R1=(CH2=C(CH3)-COO-(CH2)3-:CH2=CH-=2:10), R2=CH3-인 케이지 개열형 실록산수지 혼합물의 GPC 차트이다.8 is R 1 = (CH 2 = C (CH 3) -COO- (CH 2) 3 -:
이하, 실시예에 근거하여 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described more specifically based on examples.
<실시예 1>≪ Example 1 >
교반기, 적하 깔때기, 및 온도계를 구비한 반응 용기에, 용매로서 톨루엔 150㎖와 2-프로판올(IPA) 85㎖를 넣고, 또한 염기성 촉매로서 5% 테트라메틸암모늄히드록시드 수용액(TMAH 수용액) 37.2g을 넣었다. 적하 깔때기에 톨루엔 25㎖와 트리메톡시비닐실란(신에츠 가가쿠 가부시키가이샤 제품 KBM1OO3) 50.3g을 넣고, 반응 용기를 교반하면서 실온에서 트리메톡시비닐실란의 톨루엔 용액을 3시간 동안 적하하였다. 트리메톡시비닐실란 적하 종료 후 실온에서 2시간 교반하였다. 1시간 교반 후 교반을 정지하여 1일 정치(靜置)하였다. 반응 용액을 10% 구연산 수용액 23.0g으로 중화한 후 포화 식염수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 중축합물을 20.6g, 수율 77%로 얻었다. 이 중축합물은 다양한 유기 용제에 녹기 어려운 백색 고체였다. 또한 중축합물의 GPC를 측정한 결과, 수평균분자량은 Mn1188, 분자량 분산도(Mw/Mn)는 2.03이었다.150 ml of toluene and 85 ml of 2-propanol (IPA) were placed in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, and 37.2 g of a 5% tetramethylammonium hydroxide aqueous solution (aqueous TMAH solution) Respectively. 25 ml of toluene and 50.3 g of trimethoxyvinylsilane (KBM1003 from Shin-Etsu Chemical Co., Ltd.) were placed in a dropping funnel, and a toluene solution of trimethoxyvinylsilane was added dropwise at room temperature for 3 hours while stirring the reaction vessel. After completion of dropwise addition of trimethoxyvinylsilane, the mixture was stirred at room temperature for 2 hours. After stirring for 1 hour, stirring was stopped and allowed to stand for one day. The reaction solution was neutralized with 23.0 g of 10% citric acid aqueous solution, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 20.6 g of a polycondensate at a yield of 77%. This polycondensate was a white solid which was difficult to dissolve in various organic solvents. The GPC of the polycondensate was measured. As a result, the number-average molecular weight was Mn1188 and the molecular weight dispersion (Mw / Mn) was 2.03.
다음으로 교반기, 딘스타크(Dean-Stark), 냉각관, 및 온도계를 구비한 반응 용기에 상기에서 얻어진 중축합물 15.0g과 톨루엔 380㎖와 5% TMAH 수용액 1.72g을 넣고 120℃에서 물을 증류 제거하면서 톨루엔을 환류 가열하여 재축합 반응을 행하였다. 톨루엔 환류 후 3시간 교반한 후 실온으로 되돌려 반응을 종료하였다. 반응 용액을 10% 구연산 23.0g으로 중화한 후 포화 식염수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 재축합물을 14.5g 얻었다. 얻어진 재축합물은 백색 고체로 다양한 용매에 난용성(難溶性)을 나타내었다. 이 재축합물의 GPC를 측정한 결과를 도 1에 나타낸다. [R1SiO1.5]n으로 표현되는 재축합물 중, n이 13 이상인 케이지형 실록산, 래더(ladder)형 실록산, 및 랜덤형 실록산을 포함하는 피크 1[수평균분자량 Mn1979(Mw/Mn = 2.03)]과 n이 12 이하인 케이지형 실록산을 포함하는 피크 2[수평균분자량 Mn747(Mw/Mn = 1.02)]가 얻어졌다.Next, 15.0 g of the polycondensate obtained above, 380 ml of toluene and 1.72 g of 5% aqueous TMAH were added to a reaction vessel equipped with a stirrer, Dean-Stark, a cooling tube and a thermometer, and water was distilled off Toluene was refluxed to effect a recondensation reaction. After refluxing with toluene, the reaction mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 23.0 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 14.5 g of a recondensate. The obtained recrystallized product was a white solid and showed poor solubility in various solvents. The results of measurement of GPC of this recondensate are shown in Fig. [R 1 SiO 1.5] of the re-condensation product, which is represented by n, n is 13 or more cage-siloxane, a ladder (ladder) type siloxane, and a peak including a random-type siloxane 1 [number average molecular weight Mn1979 (Mw / Mn = 2.03 ) And a peak 2 (number average molecular weight Mn 747 (Mw / Mn = 1.02)) containing a cage siloxane having n of 12 or less was obtained.
이어서, 교반기, 딘스타크, 및 냉각관을 구비한 반응 용기에 상기에서 얻어진 재축합물 14.5g, 톨루엔 300㎖, 5% TMAH 수용액 3.0g, 및 1,3-디비닐-1,1,3,3-테트라메틸디실록산(TMDVDS: 신에츠 가가쿠 고교 가부시키가이샤 제품 LS-7250) 9.76g을 넣고, 120℃에서 물을 증류 제거하면서 톨루엔을 환류 가열하여 평형화 반응을 행하였다. 톨루엔 환류 후 3시간 교반한 후 실온으로 되돌려 반응을 종료하였다. 반응 용액을 10% 구연산 3.24g으로 중화한 후 포화 식염수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 목적의 케이지 개열형 실록산(혼합물) 16.9g이 수율 88%로 얻어졌다. 얻어진 케이지 개열형 실록산수지는 다양한 유기 용매에 가용(可溶)인 무색의 점성 액체였다.Next, to a reaction vessel equipped with a stirrer, a Dean Stark, and a cooling tube, 14.5 g of the recondensate obtained above, 300 ml of toluene, 3.0 g of 5% aqueous TMAH, 9.76 g of 3-tetramethyldisiloxane (TMDVDS: LS-7250 available from Shin-Etsu Chemical Co., Ltd.) was added and toluene was heated under reflux while water was distilled off at 120 ° C to carry out equilibration reaction. After refluxing with toluene, the reaction mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 3.24 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 16.9 g of the desired cage-cleavable siloxane (mixture) at a yield of 88%. The obtained cage-cleavable siloxane resin was a colorless viscous liquid soluble in various organic solvents.
이 케이지 개열형 실록산수지의 GPC를 측정한 결과를 도 2에 나타낸다. 케이지 개열형 실록산수지의 수평균분자량은 MnlO49(피크 3:Mw/Mn = 1.17)로 얻어졌다. 디실록산화합물의 평형화 반응에 의해 재축합물의 피크 1(Mn1979)은 저분자측으로 시프트하고, 피크 2(Mn747)가 고분자측으로 시프트하였다(피크 3). 시프트한 피크의 수평균분자량은, 재축합물의 피크 2의 수평균분자량에 디실록산화합물이 1분자 부가된 수치와 거의 일치하였다. 또한 피크 1에 관해서는, [R1SiO1.5]n의 n이 13 이상인 큰 화합물이며, 평형화 반응 중의 가열에서 실록산 결합의 절단과 결합이 반복되어 n이 작아져, 이것과 디실록산화합물이 반응했다고 생각된다. 이 결과로부터, 케이지 개열형 실록산수지는, 중축합물의 케이지를 형성하는 실록산 결합의 일부분이 절단되어 디실록산화합물과 반응함으로써 얻어진 것을 알 수 있다.The results of measurement of the GPC of this cage-cleavable siloxane resin are shown in Fig. The number average molecular weight of the cage-cleaved siloxane resin was MnlO49 (peak 3: Mw / Mn = 1.17). Peak 1 (Mn1979) of the recondensate was shifted to the low molecular side by the equilibration reaction of the disiloxane compound, and peak 2 (Mn747) shifted toward the polymer side (peak 3). The number average molecular weight of the shifted peak almost coincided with the number obtained by adding one molecule of the disiloxane compound to the number average molecular weight of
또한 상기에서 얻어진 케이지 개열형 실록산수지의 1H-NMR을 측정한 바, 6.2~5.7ppm의 비닐기에 의한 5.8~6.2ppm의 멀티플렛(multiplet) 피크와, 0.17ppm의 메틸기에 의한 피크 적분비는, 비닐기 15.4에 대하여 메틸기 6이었다.As a result of 1 H-NMR measurement of the cage-cleavable siloxane resin obtained above, peak multiplication by a multiplet peak of 5.8 to 6.2 ppm by a vinyl group of 6.2 to 5.7 ppm and a methyl group of 0.17 ppm, Methyl group was 6 for the vinyl group of 15.4.
또한 얻어진 케이지 개열형 실록산수지를 액체 크로마토그래피 대기압 이온화 분석계(LC/APCI-MS)에 의해 질량 분석을 행한 결과를 도 3에 나타낸다. 그와 더불어, 표 1에는 질량 분석하여 검출된 주된 피크와, 그에 상당하는 화학식(2)의 m, n에 해당하는 수치를 정리하여 나타낸다. 검출되는 피크 m/z는 하기 일반식(2)(단, m이 1~4, n이 8~16이고, m과 n의 합이 10~20)로 표현되는 케이지 개열형 실록산수지의 분자량에 암모늄 이온이 부가된 값이다. 이 질량 분석 결과로부터도 케이지 개열형 실록산수지는, 중축합물의 케이지를 형성하는 실록산 결합의 일부분이 절단되어 디실록산화합물과 반응함으로써 얻어진 것을 알 수 있다.The obtained cage-cleavable siloxane resin was subjected to mass analysis by a liquid chromatography atmospheric pressure ionization analyzer (LC / APCI-MS), and the results are shown in Fig. In addition, Table 1 summarizes the main peak detected by mass spectrometry and numerical values corresponding to m and n in Equation (2) corresponding thereto. The peak m / z to be detected is represented by the molecular weight of the cage-cleavable siloxane resin represented by the following general formula (2) (wherein m is 1 to 4, n is 8 to 16 and the sum of m and n is 10 to 20) Ammonium ion added value. From the results of the mass analysis, it was also found that the cage-cleavable siloxane resin was obtained by partially cleaving a siloxane bond forming the cage of the polycondensate and reacting with the disiloxane compound.
<실시예 2>≪ Example 2 >
실시예 1과 마찬가지로, 교반기, 적하 깔때기, 및 온도계를 구비한 반응 용기에 톨루엔 384㎖, 5% TMAH 수용액 40.0g, 2-프로판올(IPA) 192㎖, 트리메톡시비닐실란 43.6g, 트리메톡시메틸실란 47.4g, 및 IPA 128㎖의 용액을 3시간 동안 적하한 후 3시간 실온(20~25℃)에서 교반하였다. 이 반응 용액을 1일 정치하였다. 반응 용액은 10% 구연산 수용액으로 중화한 후 포화 식염수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 메틸기와 비닐기를 가지는 중축합물 46.6g을 수율 80%로 얻었다. 이 중축합물의 GPC를 측정한 결과, 수평균분자량은 Mn1447(Mw/Mn = 31.5)이었다.In the same manner as in Example 1, 384 ml of toluene, 40.0 g of 5% TMAH aqueous solution, 192 ml of 2-propanol (IPA), 43.6 g of trimethoxyvinylsilane, 47.4 g of methylsilane and 128 ml of IPA was added dropwise over 3 hours, followed by stirring at room temperature (20 to 25 ° C) for 3 hours. This reaction solution was allowed to stand for one day. The reaction solution was neutralized with 10% citric acid aqueous solution, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 46.6 g of a polycondensate having a methyl group and a vinyl group in a yield of 80%. As a result of GPC measurement of this polycondensate, the number average molecular weight was Mn1447 (Mw / Mn = 31.5).
다음으로 교반기, 딘스타크, 냉각관, 및 온도계를 구비한 반응 용기에 상기에서 얻어진 중축합물 15.0g과 톨루엔 380㎖와 5% TMAH 수용액 1.72g을 넣고 120℃에서 물을 증류 제거하면서 톨루엔을 환류 가열하여 재축합 반응을 행하였다. 톨루엔 환류 후 3시간 교반한 후 실온으로 되돌려 반응을 종료하였다. 반응 용액을 10% 구연산 23.0g으로 중화한 후 포화 식염수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 재축합물을 14.5g 얻었다. 얻어진 재축합물은 무색 투명 액체가 얻어졌다. 이 재축합물의 GPC를 측정한 결과를 도 4에 나타낸다. [R1SiO1.5]n으로 표현되는 재축합물 중 n이 13 이상인 케이지형 실록산, 래더형 실록산, 및 랜덤형 실록산을 포함하는 피크 4[수평균분자량 Mn1676(Mw/Mn = 1.27)]와 n이 12 이하인 케이지형 실록산인 것을 포함하는 피크 5[수평균분자량 Mn645(Mw/Mn = 1.02)]가 얻어졌다. 단, 재축합물 [R1SiO1.5]n에서의 R1은 비닐기만을 가지는 것, 메틸기만을 가지는 것, 비닐기와 메틸기의 2종류를 가지는 것을 포함한다.Next, 15.0 g of the polycondensate obtained above, 380 ml of toluene and 1.72 g of 5% aqueous TMAH were added to a reaction vessel equipped with a stirrer, a Dean Stark, a cooling tube and a thermometer, and water was distilled off at 120 ° C. And the re-condensation reaction was carried out. After refluxing with toluene, the reaction mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 23.0 g of 10% citric acid, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 14.5 g of a recondensate. The obtained recondensate was a colorless transparent liquid. The results of measurement of GPC of this recondensate are shown in Fig. (Number average molecular weight Mn 1676 (Mw / Mn = 1.27)) containing cage siloxane having n of not less than 13, ladder siloxane and random siloxane among the recondensations represented by [R 1 SiO 1.5 ] n and n (Number average molecular weight Mn645 (Mw / Mn = 1.02)), which is a cage siloxane having a number average molecular weight of 12 or less, was obtained. However, the re-condensation product [R 1 SiO 1.5] n R 1 in include those with those which would have a vinyl deception, only a methyl group, and two kinds of vinyl group and methyl group.
상기에서 얻어진 재축합물 10g, 톨루엔 342㎖, 5% TMAH 수용액 3.0g 및 TMDVDS 9.6g을 교반기, 딘스타크 및 냉각관을 구비한 반응 용기에 넣고, 120℃에서 물을 증류 제거하면서 톨루엔을 환류 가열하여 가수분해 부가 반응을 행하였다. 톨루엔 환류하면서 3시간 교반한 후 실온으로 되돌려 반응을 종료하였다. 반응 용액을 10% 구연산 1.2g으로 중화한 후 증류수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 목적의 케이지 개열형 실록산수지 11.4g을 수율 86%로 얻었다. 얻어진 케이지 개열형 실록산수지는 다양한 유기 용매에 가용인 무색의 점성 액체였다. 이 케이지 개열형 실록산수지의 GPC를 측정한 결과를 도 5에 나타낸다. 케이지 개열형 실록산의 수평균분자량은 Mn928(피크 6: Mw/Mn = 1.16)로 얻어졌다.10 g of the recondensate obtained above, 342 ml of toluene, 3.0 g of 5% TMAH aqueous solution and 9.6 g of TMDVDS were placed in a reaction vessel equipped with a stirrer, a Dean Stark and a cooling tube. While water was distilled off at 120 ° C, And the hydrolyzed part was reacted. After stirring for 3 hours while refluxing with toluene, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 1.2 g of 10% citric acid, washed with distilled water and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 11.4 g of the desired cage-cleavable siloxane resin in a yield of 86%. The resulting cage-cleavable siloxane resin was a colorless viscous liquid soluble in various organic solvents. The results of measurement of GPC of this cage-cleavable siloxane resin are shown in Fig. The number-average molecular weight of the cage-cleaved siloxane was Mn 928 (peak 6: Mw / Mn = 1.16).
<실시예 3>≪ Example 3 >
실시예 1과 동일하게 하여 얻은 재축합물 7.95g, 헥사메틸디실록산 1.41g, 5% TMAH 수용액 0.47g 및 톨루엔 50㎖를 교반기, 딘스타크 및 냉각관을 구비한 반응 용기에 넣고, 80℃에서 3시간 교반한 후 100℃로 승온하여 1.5시간, 또한 130℃로 승온하여 1.5시간 교반하였다. 반응 용액을 실온으로 되돌려 구연산, 10% 구연산 3.24g으로 중화한 후 포화 식염수로 세정하고 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 목적의 케이지 개열형 실록산수지 9.45g을 수율 94%로 얻었다. 얻어진 케이지 개열형 실록산은 다양한 유기 용매에 가용인 무색의 점성 액체였다. 이 케이지 개열형 실록산수지의 GPC를 측정한 결과를 도 6에 나타낸다. 케이지 개열형 실록산수지의 수평균분자량은 Mn939(피크 7: Mw/Mn = 1.12)로 얻어졌다.7.95 g of the recondensate obtained in the same manner as in Example 1, 1.41 g of hexamethyldisiloxane, 0.47 g of 5% aqueous TMAH and 50 ml of toluene were placed in a reaction vessel equipped with a stirrer, a Dean Stark and a cooling tube, After stirring for 3 hours, the temperature was raised to 100 占 폚, and the temperature was raised to 130 占 폚 for 1.5 hours and stirred for 1.5 hours. The reaction solution was returned to room temperature and neutralized with 3.24 g of citric acid and 10% citric acid, followed by washing with saturated brine and dehydration with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 9.45 g of the desired cage-cleavable siloxane resin in a yield of 94%. The obtained cage cleavage type siloxane was a colorless viscous liquid soluble in various organic solvents. The results of measurement of the GPC of this cage-cleavable siloxane resin are shown in Fig. The number average molecular weight of the cage-cleavable siloxane resin was Mn 939 (peak 7: Mw / Mn = 1.12).
<실시예 4><Example 4>
실시예 1과 동일하게 하여 얻은 재축합물 5.00g, 1,3-디(3-글리시독시프로필)-1,1,3,3-테트라메틸디실록산(신에츠 가가쿠 고교 가부시키가이샤 제품 LS-7970) 2.28g, 5% TMAH 수용액 1.14g 및 톨루엔 63㎖를 교반기, 딘스타크 및 냉각관을 구비한 반응 용기에 넣고, 120℃에서 물을 증류 제거하면서 톨루엔을 환류 가열해 톨루엔을 환류하여 재축합 반응을 행하였다. 톨루엔 환류 후 5시간 교반한 후 실온으로 되돌려 반응을 종료하였다. 반응 용액을 포화 식염수로 세정하고, 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 목적의 케이지 개열형 실록산수지, 재축합물, 및 1,3-비스(글리시독시프로필)-1,1,3,3-테트라메틸디실록산의 반응 혼합물 6.48g을 수량(收量) 89%로 얻었다. GPC에 있어서 원료인 디실록산의 피크(피크 9: Mn357)와, 케이지 개열형 실록산과 재축합물을 포함하는 피크(피크 8: Mn1242)를 확인할 수 있었다. 얻어진 반응 혼합물은 다양한 유기 용매에 가용인 투명의 점성 액체였다. 이 반응 혼합물의 GPC를 측정한 결과를 도 7에 나타낸다.(3-glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., LS, manufactured by Shin-Etsu Chemical Co., Ltd.) -7970), 1.14 g of a 5% TMAH aqueous solution and 63 ml of toluene were placed in a reaction vessel equipped with a stirrer, a Dean Stark and a cooling tube, and toluene was refluxed while distilling off water at 120 ° C to reflux toluene A condensation reaction was carried out. After refluxing with toluene, the reaction mixture was stirred for 5 hours and then returned to room temperature to complete the reaction. The reaction solution was washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain the desired cage-cleavable siloxane resin, the recondensate and a reaction mixture of 1,3-bis (glycidoxypropyl) -1,1,3,3-tetramethyldisiloxane 6.48 g was obtained in yield of 89%. A peak (peak 9: Mn357) of disiloxane as a raw material in the GPC and a peak (peak 8: Mn1242) including a recrystallization-type siloxane and a recondensate were confirmed. The obtained reaction mixture was a transparent viscous liquid soluble in various organic solvents. The results of measuring the GPC of this reaction mixture are shown in Fig.
<실시예 5>≪ Example 5 >
실시예 1과 동일하게 하여 얻은 재축합물 4.00g, 1,3-디(3-메타크릴옥시프로필)-1,1,3,3-테트라메틸디실록산 2.27g, 5% TMAH 수용액 1.07g 및 톨루엔 60㎖를 교반기, 딘스타크 및 냉각관을 구비한 반응 용기에 넣고, 120℃에서 물을 증류 제거하면서 톨루엔을 환류 가열하여 재축합 반응을 행하였다. 톨루엔 환류 후 5시간 교반한 후 실온으로 되돌려 반응을 종료하였다. 반응 용액을 포화 식염수로 세정하고, 무수 황산마그네슘으로 탈수하였다. 무수 황산마그네슘을 여과 분별하고, 농축함으로써 목적의 케이지 개열형 실록산수지와 재축합물, 1,3-디(3-메타크릴옥시프로필)-1,1,3,3-테트라메틸디실록산의 반응 혼합물 5.51g을 수량 91%로 얻었다. GPC에 있어서 원료인 디실록산의 피크(피크 11: Mn422)와, 케이지 개열형 실록산수지와 재축합물을 포함하는 피크(피크 10: Mn1122)를 확인할 수 있었다. 얻어진 케이지 개열형 실록산수지를 포함하는 반응 혼합물은 다양한 유기 용매에 가용인 투명의 점성 액체였다. 이 반응 혼합물의 GPC를 측정한 결과를 도 8에 나타낸다.4.00 g of the recondensate obtained in the same manner as in Example 1, 2.27 g of 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1.07 g of 5% aqueous TMAH, 60 ml of toluene was placed in a reaction vessel equipped with a stirrer, a Dean Stark and a cooling tube, and toluene was heated under reflux while water was distilled off at 120 ° C to carry out a condensation reaction. After refluxing with toluene, the reaction mixture was stirred for 5 hours and then returned to room temperature to complete the reaction. The reaction solution was washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain the objective cage-cleavable siloxane resin and the recondensate, the reaction of 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane 5.51 g of a mixture was obtained in a yield of 91%. (Peak 11: Mn 422) as the raw material in the GPC and a peak (peak 10: Mn 1122) including the cement-cleaved siloxane resin and the recondensate were confirmed. The reaction mixture containing the obtained cage cleavage type siloxane resin was a transparent viscous liquid soluble in various organic solvents. The results of GPC measurement of this reaction mixture are shown in FIG.
상기의 실시예 1~5에 있어서, 재축합물에 디실록산화합물을 평형화 반응시키는 반응시의 투입량을 이하의 표 2에 정리하여 나타낸다.In the above Examples 1 to 5, the amount of the reaction during the reaction in which the disiloxane compound is subjected to equilibration reaction in the recondensate is summarized in Table 2 below.
또한 하기 표 3에는, 상기 실시예 1~5에 있어서 얻어진 케이지 개열형 실록산수지의 GPC 계산 결과를 정리하여 나타낸다. 디실록산화합물의 평형화 반응에 의해 재축합물의 피크 1(Mn1979)은 저분자측으로 시프트하고, 피크 2(Mn747)가 고분자측으로 시프트하였다. 시프트한 피크의 수평균분자량은, 재축합물의 피크 2의 수평균분자량에 디실록산화합물이 1분자 부가된 수치와 거의 일치하였다. 또한 피크 1에 관해서는, [R1SiO1.5]n의 n이 13 이상인 큰 화합물로서, 평형화 반응 중의 가열에서 실록산 결합의 절단과 결합이 반복되어 n이 작아져, 이것에 디실록산화합물이 부가되었다고 생각된다. 이들 결과로부터 실시예 1~5에서 얻어진 케이지 개열형 실록산수지는, 중축합물의 케이지를 형성하는 실록산 결합의 일부분이 절단되어 디실록산화합물과 반응함으로써 얻어진 것을 알 수 있다.In Table 3, GPC calculation results of the cage-cleavable siloxane resin obtained in Examples 1 to 5 are summarized. Peak 1 (Mn1979) of the recondensate was shifted to the low molecular side by the equilibration reaction of the disiloxane compound, and peak 2 (Mn747) shifted toward the polymer side. The number average molecular weight of the shifted peak almost coincided with the number obtained by adding one molecule of the disiloxane compound to the number average molecular weight of
또한 상기 실시예 1~5에서 얻어진 케이지 개열형 실록산과 그 외의 실록산수지(11)~(14)의 상용성을 확인하였다. 결과를 표 4에 나타낸다. 이 결과로부터, 재축합물인 케이지상 실록산은 결정성이 높고, 다른 실록산수지와의 상용성은 거의 없지만, 평형화 반응에 의해 케이지형 구조의 일부의 실록산 결합을 개열한 케이지 개열형 실록산수지에서는, 다른 실록산수지와의 상용성이 크게 향상한 것을 알 수 있다. 또한 표 4에서의 기호는, "○: 상용성이 있음, ×: 상용성이 없음"을 나타낸다. 또한 상용성을 확인한 실록산수지(11), (12), (13), (14)는 하기에 나타내는 일반식으로 표현되는 화합물이다.The compatibility of the cage-cleavable siloxane obtained in Examples 1 to 5 with other siloxane resins (11) to (14) was also confirmed. The results are shown in Table 4. From these results, it was found that the cage siloxane resin, which is a recondensate, has high crystallinity and has almost no compatibility with other siloxane resins. However, in the cage-cleavable siloxane resin in which part of the siloxane bonds of the cage- It can be seen that the compatibility with the resin is greatly improved. In addition, symbols in Table 4 indicate "◯: compatibility, ×: no compatibility". The siloxane resins (11), (12), (13), and (14) having compatibility confirmed are compounds represented by the following general formulas.
또한 하기의 표 5에는, 상기 실시예 1~5에 있어서 얻어진 케이지 개열형 실록산수지의 GPC 차트에 있어서, 원료인 디실록산화합물을 제외한 피크 3, 6, 7, 8, 10을 곡(谷) 피크로 분할하여 재계산을 행하여, 일반식(2)In the following Table 5, the
(단, m이 1~4, n이 8~16이고, m과 n의 합이 10~20)에 상당하는 분자량 범위의 수평균분자량과 그 면적 비율을 정리한 결과를 나타낸다.Average molecular weight in the molecular weight range corresponding to the number of moles (where m is from 1 to 4, n is from 8 to 16 and the sum of m and n is from 10 to 20).
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