JP2021024791A - Allyl isocyanurate compound and method for synthesizing the same - Google Patents
Allyl isocyanurate compound and method for synthesizing the same Download PDFInfo
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- JP2021024791A JP2021024791A JP2019142717A JP2019142717A JP2021024791A JP 2021024791 A JP2021024791 A JP 2021024791A JP 2019142717 A JP2019142717 A JP 2019142717A JP 2019142717 A JP2019142717 A JP 2019142717A JP 2021024791 A JP2021024791 A JP 2021024791A
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- isocyanurate compound
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- -1 Allyl isocyanurate compound Chemical class 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 68
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 26
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000005905 mesyloxy group Chemical group 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 3
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 claims description 3
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000003431 cross linking reagent Substances 0.000 description 11
- 239000003607 modifier Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XVNBMCIQCILWHP-UHFFFAOYSA-N 1,3,5-tris(2-chloroethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound ClCCN1C(=O)N(CCCl)C(=O)N(CCCl)C1=O XVNBMCIQCILWHP-UHFFFAOYSA-N 0.000 description 2
- FKBYRZCVXYSLEL-UHFFFAOYSA-N 1h-triazine-4,5,6-trione Chemical group O=C1NN=NC(=O)C1=O FKBYRZCVXYSLEL-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical class CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C(N(*1*C1)C(CC(C(C)=O)=C*)=O)=O)=C Chemical compound CC(C(N(*1*C1)C(CC(C(C)=O)=C*)=O)=O)=C 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical group C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本発明は、新規なアリルイソシアヌレート化合物およびその合成方法に関する。 The present invention relates to novel allyl isocyanurate compounds and methods for synthesizing them.
アリルイソシアヌレート化合物を電子材料分野において用いられる樹脂の架橋剤や改質剤として用いた場合には、同化合物の有するリジッドなトリアジン骨格が、樹脂を構成する重合体の分子中に取り込まれることにより、樹脂の機械的強度、寸法安定性、耐熱性、耐薬品性、耐加水分解性、耐候性（耐光性）、難燃性、電気的特性等を改善することができる。そのため、樹脂が使用される用途や、樹脂に求められる特性に応じて、数多くの種類のアリルイソシアヌレート化合物が開発・検討され、また実用にも供されている。 When an allyl isocyanurate compound is used as a cross-linking agent or a modifier for a resin used in the field of electronic materials, the rigid triazine skeleton of the compound is incorporated into the molecules of the polymer constituting the resin. , Mechanical strength, dimensional stability, heat resistance, chemical resistance, hydrolysis resistance, weather resistance (light resistance), flame retardancy, electrical characteristics, etc. of the resin can be improved. Therefore, many kinds of allyl isocyanurate compounds have been developed and studied according to the application in which the resin is used and the characteristics required for the resin, and are also put into practical use.
また、アリルイソシアヌレート化合物は、リチウムイオン二次電池等の非水電解質二次電池の電解液添加剤として有用であることが報告されており、保存特性やサイクル特性を向上させるための添加剤として検討されている。 Further, it has been reported that the allyl isocyanurate compound is useful as an electrolyte solution additive for non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries, and as an additive for improving storage characteristics and cycle characteristics. It is being considered.
本発明に関連する従来技術について、文献を引用して以下に述べる。
特許文献１に記載された発明は、２以上のトリアジントリオン構造を有するアルケニル化合物に関するものである。
この文献には、２以上のトリアジントリオン構造を有するアルケニル化合物の例として、化学式（Ｒｅｆ−１）および（Ｒｅｆ−２）で示される化合物が記載されている。当該アルケニル化合物は構造中にヒドロキシ基を含むため、電子材料分野において用いられる樹脂の架橋剤や改質剤として用いた場合には、極性の高いヒドロキシ基による影響で樹脂の電気的特性が悪化したり、水分との親和性の高いヒドロキシ基による影響で樹脂の耐加水分解性が悪化したりするという問題があった。また、非水電解質二次電池の電解液添加剤として用いた場合には、非水電解質二次電池の負極においてヒドロキシ基のプロトンが電気化学的に還元されて水素ガスが発生することにより、保存時やサイクル時における電池の膨れの要因になるという問題があった。
The prior art related to the present invention will be described below with reference to the literature.
The invention described in Patent Document 1 relates to an alkenyl compound having two or more triazine trione structures.
This document describes compounds represented by the chemical formulas (Ref-1) and (Ref-2) as examples of alkenyl compounds having two or more triazine trione structures. Since the alkenyl compound contains a hydroxy group in its structure, when it is used as a cross-linking agent or a modifier for a resin used in the field of electronic materials, the electrical properties of the resin deteriorate due to the influence of the highly polar hydroxy group. In addition, there is a problem that the hydrolysis resistance of the resin is deteriorated due to the influence of the hydroxy group having a high affinity with water. Further, when used as an electrolyte solution additive for a non-aqueous electrolyte secondary battery, it is preserved by electrochemically reducing the proton of the hydroxy group at the negative electrode of the non-aqueous electrolyte secondary battery to generate hydrogen gas. There was a problem that it became a factor of battery swelling during time and cycle.
特許文献２に記載された発明は、ビス（ジアリルイソシアヌレート）化合物の製造方法に関するものである。
この文献には、ビス（ジアリルイソシアヌレート）化合物の例として、化学式（Ｒｅｆ−３）で示されるトリメチレンビス（ジアリルイソシアヌレート）および化学式（Ｒｅｆ−４）で示されるテトラメチレンビス（ジアリルイソシアヌレート）とそれらの合成方法が記載されている。
The invention described in Patent Document 2 relates to a method for producing a bis (diallyl isocyanurate) compound.
In this document, as examples of bis (diallyl isocyanurate) compounds, trimethylenebis (diallyl isocyanurate) represented by the chemical formula (Ref-3) and tetramethylenebis (diallyl isocyanurate) represented by the chemical formula (Ref-4) are described. ) And how to synthesize them.
本発明は、構造中にヒドロキシ基を有しない新規なアリルイソシアヌレート化合物およびその合成方法を提供することを目的とする。 An object of the present invention is to provide a novel allyl isocyanurate compound having no hydroxy group in its structure and a method for synthesizing the allyl isocyanurate compound.
本発明者等は、このような事情に鑑み鋭意研究を重ねた結果、化学式（４）で示されるイソシアヌレート化合物と化学式（６）で示されるジアリルイソシアヌレート化合物を反応させることにより、所期の目的を達成し得ることを見出し、本発明を完遂するに至ったものである。
即ち、第１の発明は、化学式（１）で示されるアリルイソシアヌレート化合物である。
As a result of diligent research in view of such circumstances, the present inventors have made the desired reaction between the isocyanurate compound represented by the chemical formula (4) and the diallyl isocyanurate compound represented by the chemical formula (6). It has been found that the object can be achieved, and the present invention has been completed.
That is, the first invention is an allyl isocyanurate compound represented by the chemical formula (1).
第２の発明は、化学式（４）で示されるイソシアヌレート化合物と、化学式（６）で示されるジアリルイソシアヌレート化合物とを、塩基の存在下にて反応させることを特徴とする、第１の発明のアリルイソシアヌレート化合物の合成方法である。 The second invention is characterized in that the isocyanurate compound represented by the chemical formula (4) is reacted with the diallyl isocyanurate compound represented by the chemical formula (6) in the presence of a base. This is a method for synthesizing an allyl isocyanurate compound.
本発明のアリルイソシアヌレート化合物は、樹脂の架橋剤や改質剤、または電池の添加剤等として利用が期待される。また、本発明の合成方法によれば、低廉な原料を用いて、簡単な操作によって高収率かつ高純度にて、目的とするアリルイソシアヌレート化合物を得ることができる。 The allyl isocyanurate compound of the present invention is expected to be used as a cross-linking agent or modifier for a resin, an additive for a battery, or the like. Further, according to the synthesis method of the present invention, the desired allyl isocyanurate compound can be obtained in high yield and high purity by a simple operation using an inexpensive raw material.
本発明のアリルイソシアヌレート化合物は、前記化学式（１）に示されるとおり、イソシアヌレート骨格に、２または３個のジアリルイソシアヌレート環類の各々が、ある種のアルキレン基を介して結合した構造を有する。 As shown in the chemical formula (1), the allyl isocyanurate compound of the present invention has a structure in which each of two or three diallyl isocyanurate rings is bonded to the isocyanurate skeleton via a certain alkylene group. Have.
前記化学式（１）および化学式（３）においてＡで示される基は、前記化学式（２）で示されるアリル基類を表す。例えば、アリル基、２−メチルアリル基（メタリル基）、３−メチルアリル基、２，３−ジメチルアリル基、３，３−ジメチルアリル基、２，３，３−トリメチルアリル基が挙げられ、好ましくはアリル基が挙げられる。 The group represented by A in the chemical formula (1) and the chemical formula (3) represents an allyl group represented by the chemical formula (2). For example, an allyl group, a 2-methylallyl group (metharyl group), a 3-methylallyl group, a 2,3-dimethylallyl group, a 3,3-dimethylallyl group, and a 2,3,3-trimethylallyl group are preferable. Allyl group is mentioned.
前記化学式（１）および化学式（３）においてＡで示される基は、互いに独立して同一であっても異なっていてもよく、互いに同一であることが好ましい。 The groups represented by A in the chemical formulas (1) and (3) may be the same or different independently of each other, and are preferably the same.
前記化学式（１）および化学式（３）においてＹで示される基は、主鎖中にエーテル結合、ベンゼン環、環状炭化水素、または不飽和結合を有していてもよい炭素数２〜１８のアルキレン基を表す。例えば、鎖状または分岐状の炭素数２〜１８のアルキレン基、主鎖中にエーテル結合を有するアルキレン基、主鎖中にベンゼン環を有するアルキレン基、主鎖中に環状炭化水素を有するアルキレン基、主鎖中に二重結合を有するアルキレン基が挙げられる。好ましくは、鎖状の炭素数２〜６のアルキレン基、鎖状の炭素数８または炭素数１０のアルキレン基、化学式（７）で示される主鎖中にエーテル結合を有するアルキレン基、ｏ−キシリレン基、ｍ−キシリレン基、ｐ−キシリレン基、ｔｒａｎｓ−ブテニレン基、ｃｉｓ−ブテニレン基が挙げられる。より好ましくは、鎖状の炭素数２〜６のアルキレン基、ｏ−キシリレン基、ｐ−キシリレン基が挙げられる。 The group represented by Y in the chemical formulas (1) and (3) is an alkylene having 2 to 18 carbon atoms which may have an ether bond, a benzene ring, a cyclic hydrocarbon, or an unsaturated bond in the main chain. Represents a group. For example, a chain or branched alkylene group having 2 to 18 carbon atoms, an alkylene group having an ether bond in the main chain, an alkylene group having a benzene ring in the main chain, and an alkylene group having a cyclic hydrocarbon in the main chain. , An alkylene group having a double bond in the main chain can be mentioned. Preferably, a chain alkylene group having 2 to 6 carbon atoms, a chain alkylene group having 8 or 10 carbon atoms, an alkylene group having an ether bond in the main chain represented by the chemical formula (7), o-xylylene. Examples thereof include a group, an m-xylylene group, a p-xylylene group, a trans-butenylene group, and a cis-butenylene group. More preferably, a chain alkylene group having 2 to 6 carbon atoms, an o-xylylene group, and a p-xylylene group can be mentioned.
前記化学式（１）および化学式（３）においてＹで示される基は、互いに独立して同一であっても異なっていてもよく、互いに同一であることが好ましい。 The groups represented by Y in the chemical formulas (1) and (3) may be the same or different independently of each other, and are preferably the same.
本発明の化学式（１）で示されるアリルイソシアヌレート化合物は、原料入手の容易性および合成プロセスの簡略化の見地から、化学式（１’）で示されるアリルイソシアヌレート化合物であることが好ましい。 The allyl isocyanurate compound represented by the chemical formula (1) of the present invention is preferably the allyl isocyanurate compound represented by the chemical formula (1') from the viewpoint of easy availability of raw materials and simplification of the synthetic process.
このようなアリルイソシアヌレート化合物の例としては、化学式（１−１）〜（１−１４）で示されるアリルイソシアヌレート化合物を好ましく挙げることができる。 As an example of such an allyl isocyanurate compound, the allyl isocyanurate compounds represented by the chemical formulas (1-1) to (1-14) can be preferably mentioned.
＜本発明のアリルイソシアヌレート化合物の合成方法について＞
前記の第２の発明として記載したとおり、本発明によるアリルイソシアヌレート化合物の合成方法は、化学式（４）で示されるイソシアヌレート化合物と、化学式（６）で示されるジアリルイソシアヌレート化合物とを、塩基の存在下にて反応させることによって、化学式（１）で示されるアリルイソシアヌレート化合物を得るものである。
<About the method for synthesizing the allyl isocyanurate compound of the present invention>
As described as the second invention described above, the method for synthesizing the allyl isocyanurate compound according to the present invention comprises using the isocyanurate compound represented by the chemical formula (4) and the diallyl isocyanurate compound represented by the chemical formula (6) as bases. By reacting in the presence of the above, the allyl isocyanurate compound represented by the chemical formula (1) is obtained.
前記化学式（４）および化学式（５）においてＸで示される基はハロゲン原子、メシルオキシ基（ＯＭｓ）、トシルオキシ基（ＯＴｓ）、またはトリフルオロメタンスルホニルオキシ基（ＯＴｆ）を表す。ハロゲン原子は、フッ素原子、塩素原子、臭素原子、またはヨウ素原子を表す。Ｘで示される基は、塩素原子、臭素原子、メシルオキシ基（ＯＭｓ）であることが好ましく、塩素原子であることがより好ましい。 The group represented by X in the chemical formula (4) and the chemical formula (5) represents a halogen atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The group represented by X is preferably a chlorine atom, a bromine atom, or a mesyloxy group (OMs), and more preferably a chlorine atom.
前記化学式（４）および化学式（５）においてＸで示される基は、互いに独立して同一であっても異なっていてもよく、互いに同一であることが好ましい。 The groups represented by X in the chemical formulas (4) and (5) may be the same or different independently of each other, and are preferably the same.
前記化学式（４）および化学式（５）においてＹで示される基は、主鎖中にエーテル結合、ベンゼン環、環状炭化水素、または不飽和結合を有していてもよい炭素数２〜１８のアルキレン基を表す。例えば、鎖状または分岐状の炭素数２〜１８のアルキレン基、主鎖中にエーテル結合を有するアルキレン基、主鎖中にベンゼン環を有するアルキレン基、主鎖中に環状炭化水素を有するアルキレン基、主鎖中に二重結合を有するアルキレン基が挙げられる。好ましくは、鎖状の炭素数２〜６のアルキレン基、鎖状の炭素数８または炭素数１０のアルキレン基、前記化学式（７）で示される主鎖中にエーテル結合を有するアルキレン基、ｏ−キシリレン基、ｍ−キシリレン基、ｐ−キシリレン基、ｔｒａｎｓ−ブテニレン基、ｃｉｓ−ブテニレン基が挙げられる。より好ましくは、鎖状の炭素数２〜６のアルキレン基、ｏ−キシリレン基、ｐ−キシリレン基が挙げられる。 The group represented by Y in the chemical formulas (4) and (5) is an alkylene having 2 to 18 carbon atoms which may have an ether bond, a benzene ring, a cyclic hydrocarbon, or an unsaturated bond in the main chain. Represents a group. For example, a chain or branched alkylene group having 2 to 18 carbon atoms, an alkylene group having an ether bond in the main chain, an alkylene group having a benzene ring in the main chain, and an alkylene group having a cyclic hydrocarbon in the main chain. , An alkylene group having a double bond in the main chain can be mentioned. Preferably, a chain alkylene group having 2 to 6 carbon atoms, a chain alkylene group having 8 or 10 carbon atoms, an alkylene group having an ether bond in the main chain represented by the chemical formula (7), o- Examples thereof include a xylylene group, an m-xylylene group, a p-xylylene group, a trans-butenylene group, and a cis-butenylene group. More preferably, a chain alkylene group having 2 to 6 carbon atoms, an o-xylylene group, and a p-xylylene group can be mentioned.
前記化学式（４）および化学式（５）においてＹで示される基は、互いに独立して同一であっても異なっていてもよく、互いに同一であることが好ましい。 The groups represented by Y in the chemical formulas (4) and (5) may be the same or different independently of each other, and are preferably the same.
前記化学式（６）においてＡで示される基は、前記化学式（２）で示されるアリル基類を表す。アリル基類としては、例えば、アリル基、２−メチルアリル基（メタリル基）、３−メチルアリル基、２，３−ジメチルアリル基、３，３−ジメチルアリル基、２，３，３−トリメチルアリル基が挙げられ、好ましくはアリル基が挙げられる。 The group represented by A in the chemical formula (6) represents an allyl group represented by the chemical formula (2). Examples of the allyl group include an allyl group, a 2-methylallyl group (metharyl group), a 3-methylallyl group, a 2,3-dimethylallyl group, a 3,3-dimethylallyl group, and a 2,3,3-trimethylallyl group. , And preferably an allyl group.
前記化学式（６）においてＡで示される基は、互いに独立して同一であっても異なっていてもよく、互いに同一であることが好ましい。 The groups represented by A in the chemical formula (6) may be the same or different independently of each other, and are preferably the same.
前記化学式（４）で示されるイソシアヌレート化合物は、例えば、米国特許４２００７４９号明細書、特開昭５２−２９０号公報に準拠して合成することができる。 The isocyanurate compound represented by the chemical formula (4) can be synthesized, for example, in accordance with US Pat. No. 4,200,629, Japanese Patent Application Laid-Open No. 52-290.
前記化学式（６）で示されるジアリルイソシアヌレート化合物は、例えば、ドイツ民主共和国５１８５８Ａ号公報に準拠して合成することができる。 The diallyl isocyanurate compound represented by the chemical formula (6) can be synthesized, for example, in accordance with the German Democratic Republic No. 51858A.
前記化学式（６）で示されるジアリルイソシアヌレート化合物は、前記化学式（４）で示されるイソシアヌレート化合物に含まれるＸで示される基１モル部に対し、通常、１．０モル部以上用いられ、１．０〜１．５モル部の範囲で用いられることが好ましい。 The diallyl isocyanurate compound represented by the chemical formula (6) is usually used in an amount of 1.0 mol part or more with respect to 1 mol part of the group represented by X contained in the isocyanurate compound represented by the chemical formula (4). It is preferably used in the range of 1.0 to 1.5 mol parts.
なお、前述の、化学式（１’）で示されるアリルイソシアヌレート化合物と同様に、原料入手の容易性および合成プロセスの簡略化の見地から、この第２の発明においては、原料として、化学式（４’）で示されるイソシアヌレート化合物と、化学式（６’）で示されるジアリルイソシアヌレート化合物とを使用することが好ましい。 Similar to the above-mentioned allyl isocyanurate compound represented by the chemical formula (1'), from the viewpoint of easy availability of raw materials and simplification of the synthetic process, the chemical formula (4) is used as the raw material in the second invention. It is preferable to use the isocyanurate compound represented by') and the diallyl isocyanurate compound represented by the chemical formula (6').
前記塩基の具体例として、アルカリ金属もしくはアルカリ土類金属の水素化物、水酸化物、炭酸塩、炭酸水素塩、アルコキシドまたは有機アミン化合物が挙げられる。例えば、水素化ナトリウム、水素化カリウム、水酸化ナトリウム、水酸化カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素ルビジウム、炭酸水素セシウム、炭酸水素マグネシウム、炭酸水素カルシウム、炭酸水素ストロンチウム、炭酸水素バリウム、ナトリウムアルコキシド、カリウムアルコキシド、トリエチルアミン等が挙げられる。好ましくは、アルカリ金属もしくはアルカリ土類金属の炭酸塩または炭酸水素塩が挙げられる。 Specific examples of the base include hydrides of alkali metals or alkaline earth metals, hydroxides, carbonates, bicarbonates, alkoxides or organic amine compounds. For example, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, lithium hydrogen carbonate, carbonic acid. Examples thereof include sodium hydrogen hydrogen, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, sodium alkoxide, potassium alkoxide, and triethylamine. Preferred are carbonates or bicarbonates of alkali metals or alkaline earth metals.
前記塩基は上記の例示に限定されるものではない。また、前記塩基は、単独で、または２種以上を組み合わせて用いられる。 The base is not limited to the above examples. In addition, the base may be used alone or in combination of two or more.
前記塩基は、化学式（６）で示されるジアリルイソシアヌレート化合物（以下、「ジアリルイソシアヌレート化合物」と云うことがある）１モル部に対して１モル部以上用いられる。 The base is used in an amount of 1 mol or more with respect to 1 mol of the diallyl isocyanurate compound represented by the chemical formula (6) (hereinafter, may be referred to as “diallyl isocyanurate compound”).
化学式（４）で示されるイソシアヌレート化合物（以下、「イソシアヌレート化合物」と云うことがある）において、Ｘが塩素原子である場合（以下、「クロライド化合物」と云うことがある）またはＸが臭素原子である場合（以下、「ブロマイド化合物」と云うことがある）であるとき、ヨウ化物塩を使用することによって、ジアリルイソシアヌレート化合物とイソシアヌレート化合物との反応を促進することができる。 In the isocyanurate compound represented by the chemical formula (4) (hereinafter, may be referred to as "isocyanurate compound"), when X is a chlorine atom (hereinafter, may be referred to as "chloride compound") or X is bromine. When it is an atom (hereinafter, may be referred to as “bromide compound”), the reaction between the diallyl isocyanurate compound and the isocyanurate compound can be promoted by using an iodide salt.
即ち、クロライド化合物をヨウ化物塩の存在下にジアリルイソシアヌレート化合物と反応させるとき、クロライド化合物における塩素原子がヨウ素原子に置換される所謂ハライド置換が起こり、その結果、生成したアイオダイド化合物はヨウ素イオンの高脱離能によって高活性であるので、ジアリルイソシアヌレート化合物との反応が促進され、一方、前記アイオダイド化合物はジアリルイソシアヌレート化合物との置換反応の後、ヨウ化物塩に戻るので、かくして、ヨウ化物塩は触媒として機能する。同様にブロマイド化合物の場合もハライド置換が起こり、反応が促進される。 That is, when the chloride compound is reacted with the diallyl isocyanurate compound in the presence of the iodide salt, so-called halide substitution occurs in which the chlorine atom in the chloride compound is replaced with the iodine atom, and as a result, the produced iodide compound is produced of iodine ions. The high desorption ability promotes the reaction with the diallyl isocyanurate compound, while the iodide compound returns to the iodide salt after the substitution reaction with the diallyl isocyanurate compound, thus iodide. The salt acts as a catalyst. Similarly, in the case of bromide compounds, halide substitution occurs and the reaction is promoted.
前記ヨウ化物塩としては、例えば、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム等のアルカリ金属ヨウ化物塩を好ましい例として挙げることができる。しかし、ヨウ化物塩は上記に限定されるものではなく、上記以外にも種々の金属塩、例えば、ヨウ化銅等も好ましい例として挙げることができる。前記ヨウ化物塩は、イソシアヌレート化合物に含まれるＸで示される基１モル部に対し、通常、０．０１〜５．０モル部、好ましくは０．０２〜０．５モル部の範囲で用いられる。 As the iodide salt, for example, an alkali metal iodide salt such as lithium iodide, sodium iodide, potassium iodide and the like can be mentioned as a preferable example. However, the iodide salt is not limited to the above, and various metal salts such as copper iodide can be mentioned as preferable examples in addition to the above. The iodide salt is usually used in the range of 0.01 to 5.0 parts, preferably 0.02 to 0.5 parts, based on 1 part of the group represented by X contained in the isocyanurate compound. Be done.
ジアリルイソシアヌレート化合物とイソシアヌレート化合物との反応は、通常、反応溶媒中で行うが、無溶媒で行うこともできる。 The reaction between the diallyl isocyanurate compound and the isocyanurate compound is usually carried out in a reaction solvent, but it can also be carried out without a solvent.
前記反応溶媒としては、前記反応を阻害しないものであれば、特に制限はなく、例えば、水、メタノール、エタノール、イソプロピルアルコール等のようなアルコール類、ヘキサン、ヘプタン等のような脂肪族炭化水素類、ベンゼン、トルエン、キシレン等のような芳香族炭化水素類、塩化メチレン、クロロホルム、四塩化炭素、クロロトリフルオロメタン、ジクロロエタン、クロロベンゼン、ジクロロベンゼン等のようなハロゲン化炭化水素類、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタン、ジエチレングリコールジメチルエーテル等のようなエーテル類、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ヘキサメチルホスホロトリアミド等のようなアミド類、ジメチルスルホキシド等のようなスルホキシド類等を挙げることができる。これら反応溶媒は単独で、または２種以上組み合わせて用いられる。 The reaction solvent is not particularly limited as long as it does not inhibit the reaction. For example, alcohols such as water, methanol, ethanol and isopropyl alcohol, and aliphatic hydrocarbons such as hexane and heptane. , Aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, etc., diethyl ether, diisopropyl ether, etc. , Ethers such as tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, etc., such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphorotriamide, etc. Examples thereof include sulfoxides such as amides and dimethylsulfoxides. These reaction solvents may be used alone or in combination of two or more.
ジアリルイソシアヌレート化合物とイソシアヌレート化合物との反応は、用いる反応溶媒にもよるが、通常、０〜２００℃の範囲、好ましくは、８０〜１３０℃の範囲の温度で行われ、反応時間は、通常、３０分から４８時間程度の範囲である。 The reaction between the diallyl isocyanurate compound and the isocyanurate compound depends on the reaction solvent used, but is usually carried out at a temperature in the range of 0 to 200 ° C., preferably in the range of 80 to 130 ° C., and the reaction time is usually in the range of 80 to 130 ° C. , 30 minutes to 48 hours.
ジアリルイソシアヌレート化合物とイソシアヌレート化合物とを前記塩基（および前記ヨウ化物塩）の存在下に反応させた後、得られた反応混合物を濾過して、固形分を除去し、かくして得られた濾液を濃縮することによって、またはかくして得られた濾液を濃縮し、更に、例えば、シリカゲルクロマトグラフィーに付すことによって、目的とするアリルイソシアヌレート化合物を得ることができる。 After reacting the diallyl isocyanurate compound and the isocyanurate compound in the presence of the base (and the iodide salt), the obtained reaction mixture was filtered to remove solids, and the filtrate thus obtained was obtained. The desired allyl isocyanurate compound can be obtained by concentrating or by concentrating the filtrate thus obtained and further subjecting it to, for example, silica gel chromatography.
このようにして得られたアリルイソシアヌレート化合物は、必要であれば、活性炭処理や再結晶操作等によって精製することができる。 The allyl isocyanurate compound thus obtained can be purified by an activated carbon treatment, a recrystallization operation or the like, if necessary.
本発明のアリルイソシアヌレート化合物は、その用途に特に制限はなく、樹脂の架橋剤や改質剤、または電池の添加剤等として利用が期待される。 The allyl isocyanurate compound of the present invention is not particularly limited in its use, and is expected to be used as a cross-linking agent or modifier for a resin, an additive for a battery, or the like.
樹脂としては、例えば、ポリフェニレンエーテル（ＰＰＥ）樹脂、シリコーン樹脂、アクリル樹脂、ゴム系ポリマー、フッ素樹脂、マレイミド樹脂が挙げられる。 Examples of the resin include polyphenylene ether (PPE) resin, silicone resin, acrylic resin, rubber-based polymer, fluororesin, and maleimide resin.
本発明のアリルイソシアヌレート化合物を架橋剤や改質剤として含むポリフェニレンエーテル（ＰＰＥ）樹脂は、銅張積層板、フレキシブル銅張積層板等への利用が期待される。 The polyphenylene ether (PPE) resin containing the allyl isocyanurate compound of the present invention as a cross-linking agent or a modifier is expected to be used for copper-clad laminates, flexible copper-clad laminates, and the like.
本発明のアリルイソシアヌレート化合物を架橋剤や改質剤として含むシリコーン樹脂は、ＬＥＤやＯＬＥＤの封止材、ＬＥＤやＯＬＥＤの反射板、シリコーン系接着剤、放熱シート、放熱グリース等への利用が期待される。 The silicone resin containing the allyl isocyanurate compound of the present invention as a cross-linking agent or modifier can be used as a sealing material for LEDs and OLEDs, reflectors for LEDs and OLEDs, silicone adhesives, heat-dissipating sheets, heat-dissipating grease, and the like. Be expected.
本発明のアリルイソシアヌレート化合物を架橋剤や改質剤として含むアクリル樹脂は、カラーレジスト、ブラックレジスト、ソルダーレジスト、ハードコート、光学用粘着剤、自動車用塗料、インクジェットインク、ナノインプリント用樹脂、ＵＶ硬化型シール剤、半導体用フォトレジスト、ドライフィルムレジスト等への利用が期待される。 The acrylic resin containing the allyl isocyanurate compound of the present invention as a cross-linking agent or modifier is a color resist, a black resist, a solder resist, a hard coat, an optical adhesive, an automobile paint, an inkjet ink, a resin for nanoimprint, and UV curing. It is expected to be used for mold sealants, photoresists for semiconductors, dry film resists, etc.
本発明のアリルイソシアヌレート化合物を架橋剤や改質剤として含むゴム系ポリマーは、太陽電池用封止剤等への利用が期待される。 The rubber-based polymer containing the allyl isocyanurate compound of the present invention as a cross-linking agent or a modifier is expected to be used as a sealing agent for solar cells and the like.
本発明のアリルイソシアヌレート化合物を架橋剤や改質剤として含むフッ素樹脂は、電線被覆材、フッ素系シール剤等への利用が期待される。 The fluororesin containing the allyl isocyanurate compound of the present invention as a cross-linking agent or a modifier is expected to be used as a wire coating material, a fluorine-based sealant, and the like.
本発明のアリルイソシアヌレート化合物を架橋剤や改質剤として含むマレイミド樹脂は、プリプレグ、繊維強化プラスチック、樹脂付銅箔、銅張積層板、プリント配線板、層間絶縁材、半導体封止材、導電性ペースト、ソルダーレジスト、粉体塗料、炭素材料、レジノイド砥石等への利用が期待される。 The maleimide resin containing the allyl isocyanurate compound of the present invention as a cross-linking agent or a modifier is a prepreg, fiber reinforced plastic, copper foil with resin, copper-clad laminate, printed wiring board, interlayer insulating material, semiconductor encapsulant, conductive. It is expected to be used for sex pastes, solder resists, powder coatings, carbon materials, resinoid abrasives, etc.
また、本発明のアリルイソシアヌレート化合物は、リチウムイオン二次電池等の非水電解質二次電池の電解液添加剤等の電池の添加剤として利用が期待される。
Further, the allyl isocyanurate compound of the present invention is expected to be used as a battery additive such as an electrolyte solution additive for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
以下、実施例により、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。
なお、実施例において使用した主原料は、以下のとおりである。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
The main raw materials used in the examples are as follows.
［主原料］
・１，３，５−トリ（２−クロロエチル）−１，３，５−トリアジン−２，４，６−トリオン：米国特許４２００７４９号明細書に準拠して合成
・１，３−ジアリル−１，３，５−トリアジン−２，４，６−トリオン：四国化成工業（株）製
[Main raw material]
1,3,5-tri (2-chloroethyl) -1,3,5-triazine-2,4,6-trione: Synthesized in accordance with US Pat. No. 4,200,629. 1,3-Diallyl-1, 3,5-Triazine-2,4,56-Trione: Made by Shikoku Kasei Kogyo Co., Ltd.
〔実施例１〕
＜１，３，５−トリス［２−（３，５−ジアリル−２，４，６−トリオキソ−１，３，５−トリアジン−１−イル）エチル］−１，３，５−トリアジン−２，４，６−トリオンの合成＞
容量１００ｍｌの３口ナスフラスコに１，３，５−トリ（２−クロロエチル）−１，３，５−トリアジン−２，４，６−トリオン６．３３ｇ（２０．０ｍｍｏｌ）、１，３−ジアリル−１，３，５−トリアジン−２，４，６−トリオン１５．０６ｇ（７２．０ｍｍｏｌ）、炭酸ナトリウム７．６３ｇ（７２．０ｍｍｏｌ）、ヨウ化ナトリウム０．６０ｇ（４．０ｍｍｏｌ）、Ｎ，Ｎ−ジメチルホルムアミド２０．０ｇを仕込み、１００℃に昇温した。１００℃到達後、２４時間撹拌した。反応溶液を濃縮し、シリカゲルカラムクロマトグラフィー（酢酸エチル／ヘキサン＝１／２（ｖ／ｖ））により精製し、１３．６９ｇの淡黄色固体を得た（収率：８２．０％）。
[Example 1]
<1,3,5-Tris [2- (3,5-diallyl-2,4,6-trioxo-1,3,5-triazine-1-yl) ethyl] -1,3,5-triazine-2 , 4,6-Trione synthesis>
1,3,5-tri (2-chloroethyl) -1,3,5-triazine-2,4,6-trione 6.33 g (20.0 mmol), 1,3-diallyl in a 100 ml 3-port eggplant flask -1,3,5-triazine-2,4,6-trione 15.06 g (72.0 mmol), sodium carbonate 7.63 g (72.0 mmol), sodium iodide 0.60 g (4.0 mmol), N, 20.0 g of N-dimethylformamide was charged and the temperature was raised to 100 ° C. After reaching 100 ° C., the mixture was stirred for 24 hours. The reaction solution was concentrated and purified by silica gel column chromatography (ethyl acetate / hexane = 1/2 (v / v)) to give 13.69 g of a pale yellow solid (yield: 82.0%).
この淡黄色固体の１ＨＮＭＲスペクトルデータは、以下のとおりであった。
・1HNMR (d6-DMSO) δ:5.78(ddt, 6H), 5.16(dd, 6H), 5.13(dd, 6H), 4.33(d, 12H), 3.99(s, 12H).
また、この淡黄色固体のＩＲスペクトルデータは、図１に示したチャートのとおりであった。これらのスペクトルデータより、得られた淡黄色固体は、化学式（１−８）で示される表題のアリルイソシアヌレート化合物であるものと同定した。
The 1 HNMR spectrum data of this pale yellow solid was as follows.
・1 1 HNMR (d 6 -DMSO) δ: 5.78 (ddt, 6H), 5.16 (dd, 6H), 5.13 (dd, 6H), 4.33 (d, 12H), 3.99 (s, 12H).
The IR spectrum data of this pale yellow solid was as shown in the chart shown in FIG. From these spectral data, the obtained pale yellow solid was identified as the allyl isocyanurate compound of the title represented by the chemical formula (1-8).
本発明のアリルイソシアヌレート化合物は、樹脂の架橋剤や改質剤、または電池の添加剤等として利用が期待される。また、本発明の合成方法によれば、簡単な操作によって高収率かつ高純度にて、目的とするアリルイソシアヌレート化合物を得ることができる。よって、本発明の産業上の利用可能性は多大である。
The allyl isocyanurate compound of the present invention is expected to be used as a cross-linking agent or modifier for a resin, an additive for a battery, or the like. Further, according to the synthesis method of the present invention, the desired allyl isocyanurate compound can be obtained in high yield and high purity by a simple operation. Therefore, the industrial applicability of the present invention is great.
Claims (2)
The allyl isocyanurate compound according to claim 1, wherein the isocyanurate compound represented by the chemical formula (4) is reacted with the diallyl isocyanurate compound represented by the chemical formula (6) in the presence of a base. Synthesis method.
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