JP2015054843A - Tetrakis(carboxyalkyl)glycolurils and application thereof - Google Patents
Tetrakis(carboxyalkyl)glycolurils and application thereof Download PDFInfo
- Publication number
- JP2015054843A JP2015054843A JP2013189535A JP2013189535A JP2015054843A JP 2015054843 A JP2015054843 A JP 2015054843A JP 2013189535 A JP2013189535 A JP 2013189535A JP 2013189535 A JP2013189535 A JP 2013189535A JP 2015054843 A JP2015054843 A JP 2015054843A
- Authority
- JP
- Japan
- Prior art keywords
- tetrakis
- glycoluril
- formula
- carboxyalkyl
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 title abstract description 21
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims description 52
- -1 carboxyethyl Chemical group 0.000 claims description 35
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 20
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 18
- 150000003672 ureas Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- KQSSATDQUYCRGS-UHFFFAOYSA-N methyl glycinate Chemical group COC(=O)CN KQSSATDQUYCRGS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UUGLSEIATNSHRI-UHFFFAOYSA-N 1,3,4,6-tetrakis(hydroxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound OCN1C(=O)N(CO)C2C1N(CO)C(=O)N2CO UUGLSEIATNSHRI-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-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
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OGFKTAMJLKHRAZ-UHFFFAOYSA-N 2,2-dimethoxyacetaldehyde Chemical compound COC(OC)C=O OGFKTAMJLKHRAZ-UHFFFAOYSA-N 0.000 description 1
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical compound NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- SHYARJUKNREDGB-UHFFFAOYSA-N 2-ethyl-5-methyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCC(C)N1 SHYARJUKNREDGB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 C*CC(C)(C)CN(C(*)(C(*)(N1CC(C)(C)CC(O)=O)N2CC(C)(C)CC(O)=O)N(CC(C)(C)CC(O)=O)C2=O)C1=O Chemical compound C*CC(C)(C)CN(C(*)(C(*)(N1CC(C)(C)CC(O)=O)N2CC(C)(C)CC(O)=O)N(CC(C)(C)CC(O)=O)C2=O)C1=O 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002413 Polyhexanide Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical class COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical group CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- DIHAURBCYGTGCV-UHFFFAOYSA-N xi-4,5-Dihydro-2,4(5)-dimethyl-1H-imidazole Chemical compound CC1CN=C(C)N1 DIHAURBCYGTGCV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本発明は、新規なテトラキス（カルボキシアルキル）グリコールウリル類とその利用、特に、エポキシ樹脂用架橋剤としての利用に関する。更に、本発明は、テトラキス（カルボキシアルキル）グリコールウリル類の製造方法とその製造のための中間体に関する。 The present invention relates to novel tetrakis (carboxyalkyl) glycolurils and their uses, in particular as crosslinkers for epoxy resins. Furthermore, the present invention relates to a method for producing tetrakis (carboxyalkyl) glycolurils and an intermediate for the production thereof.
グリコールウリル類は４個の尿素系窒素を環構造中に有するヘテロ環化合物であって、上記尿素系窒素の反応性を利用して、種々の用途や新規な機能性化合物の製造に用いられている。 Glycolurils are heterocyclic compounds having four urea nitrogens in the ring structure, and are used for various applications and production of new functional compounds by utilizing the reactivity of the urea nitrogens. Yes.
例えば、グリコールウリル類をジメトキシエタナールのようなアルデヒド類と反応させてアミノプラスチック樹脂とし、これをセルロースのための架橋剤として用いることが提案されている（特許文献１参照）。 For example, it has been proposed that glycoluril is reacted with an aldehyde such as dimethoxyethanal to form an aminoplastic resin, which is used as a crosslinking agent for cellulose (see Patent Document 1).
また、酢酸ビニルとエチレンと自己架橋性単量体からなる共重合体とテトラメチロールグリコールウリル類を含むエマルジョンを不織布のためのバインダーとして用いることが提案されている（特許文献２参照）。水溶性高分子抗菌剤であるポリヘキサメチレンビグアナイド化合物を繊維に固着させるための架橋剤として用いることも提案されている（特許文献３参照）。 It has also been proposed to use an emulsion containing a copolymer of vinyl acetate, ethylene and a self-crosslinkable monomer and tetramethylol glycoluril as a binder for a nonwoven fabric (see Patent Document 2). It has also been proposed to use a polyhexamethylene biguanide compound, which is a water-soluble polymer antibacterial agent, as a crosslinking agent for fixing to a fiber (see Patent Document 3).
一方、反応性に富むアリル基を複数、分子中に有する化合物、例えば、トリアリルイソシアヌレレートは合成樹脂や合成ゴムの架橋剤としてよく知られているが、同様に、合成樹脂や合成ゴムの架橋剤として機能する分子中に４個のアリル基を有するテトラアリルグリコールウリル類も知られている（特許文献４参照）。 On the other hand, compounds having a plurality of reactive allyl groups in the molecule, such as triallyl isocyanurate, are well known as crosslinking agents for synthetic resins and synthetic rubbers. Tetraallyl glycolurils having four allyl groups in a molecule that functions as a crosslinking agent are also known (see Patent Document 4).
分子内に複数のカルボキシル基を有する化合物も、例えば、エポキシ樹脂の架橋剤としてよく知られている。例えば、その代表例はトリス（カルボキシエチル）イソシアヌレートであって、反応性に富むカルボキシル基を分子内に３個有しており、エポキシ樹脂等の架橋剤として用いられている（特許文献５参照）。トリス（カルボキシエチル）イソシアヌレートをフラックス材料とすることも提案されている（特許文献６参照）。 A compound having a plurality of carboxyl groups in the molecule is also well known as, for example, a crosslinking agent for epoxy resins. For example, a typical example is tris (carboxyethyl) isocyanurate, which has three reactive carboxyl groups in the molecule, and is used as a crosslinking agent for epoxy resins or the like (see Patent Document 5). ). It has also been proposed to use tris (carboxyethyl) isocyanurate as a flux material (see Patent Document 6).
しかし、グリコールウリル化合物の４個の窒素原子上の水素原子が全てカルボキシアルキル基で置換された化合物は、エポキシ樹脂等の架橋剤として機能することが期待されるが、これまで知られていない。 However, a compound in which all hydrogen atoms on four nitrogen atoms of a glycoluril compound are substituted with a carboxyalkyl group is expected to function as a crosslinking agent such as an epoxy resin, but it has not been known so far.
本発明は、新規なテトラキス（カルボキシアルキル）グリコールウリル類とその利用、特に、エポキシ樹脂用架橋剤を提供することを目的とする。さらに、本発明は、テトラキス（カルボキシアルキル）グリコールウリル類の製造方法を提供することを目的とする。 An object of the present invention is to provide novel tetrakis (carboxyalkyl) glycolurils and their use, in particular, a crosslinking agent for epoxy resins. Furthermore, this invention aims at providing the manufacturing method of tetrakis (carboxyalkyl) glycoluril.
本発明によれば、一般式（Ｉ） According to the invention, the general formula (I)
（式中、ｎは０又は１を示し、Ｒ1及びＲ2はそれぞれ独立に水素原子又は低級アルキル基を示す。）
で表される１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類が提供される。
(In the formula, n represents 0 or 1, and R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group.)
1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the formula:
本発明によれば、上記１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類の利用として、エポキシ樹脂用の架橋剤が提供され、更には、そのエポキシ樹脂用架橋剤とアミン類からなる硬化剤を含むエポキシ樹脂組成物が提供される。 According to the present invention, as the use of the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril, there is provided a crosslinking agent for epoxy resin, and further from the crosslinking agent for epoxy resin and amines. An epoxy resin composition containing the curing agent is provided.
更に、本発明によれば、上記１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類の製造方法が提供される。 Furthermore, according to this invention, the manufacturing method of the said 1,3,4,6-tetrakis (carboxyalkyl) glycoluril is provided.
即ち、溶媒の存在下又は不存在下、酸の存在下に、一般式（ａ） That is, in the presence or absence of a solvent, in the presence of an acid, the general formula (a)
（式中、Ｒ1及びＲ2はそれぞれ独立に水素原子又は低級アルキル基を示す。）
で表されるジカルボニル化合物と一般式（ｂ）
(In the formula, R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group.)
And a general formula (b)
（式中、Ｒ3は低級アルキル基を示す。）
で表される尿素誘導体を反応させることを含む一般式（II）
(In the formula, R 3 represents a lower alkyl group.)
Which comprises reacting a urea derivative represented by the general formula (II)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表される１，３，４，６−テトラキス（カルボキシメチル）グリコールウリル類の製造方法が提供される。
(In the formula, R 1 and R 2 are the same as described above.)
The manufacturing method of 1,3,4,6-tetrakis (carboxymethyl) glycoluril represented by these is provided.
また、溶媒の存在下又は不存在下、塩基の存在下に、一般式（ｃ） In the presence or absence of a solvent, in the presence of a base, the compound represented by the general formula (c)
（式中、Ｒ1及びＲ2はそれぞれ独立に水素原子又は低級アルキル基を示す。）
で表されるグリコールウリル類とアクリロニトリルを反応させて、一般式（ｄ）
(In the formula, R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group.)
Is reacted with acrylonitrile represented by the general formula (d)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表される１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を得る第１工程、次いで、溶媒の存在下又は不存在下、酸の存在下に、上記１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を加水分解する第２工程を含む一般式（III）
(In the formula, R 1 and R 2 are the same as described above.)
In the first step of obtaining 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril represented by the following, then in the presence or absence of a solvent, in the presence of an acid, the above 1,3,4 , 6-Tetrakis (2-cyanoethyl) glycoluril having the second step of hydrolyzing the general formula (III)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表される１，３，４，６−テトラキス（カルボキシエチル）グリコールウリル類の製造方法が提供される。
(In the formula, R 1 and R 2 are the same as described above.)
The manufacturing method of 1,3,4,6-tetrakis (carboxyethyl) glycoluril represented by these is provided.
上述したほか、本発明によれば、上記１，３，４，６−テトラキス（カルボキシエチル）グリコールウリル類の製造のための中間体である前記一般式（ｄ）で表される１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類が提供される。 In addition to the above, according to the present invention, 1,3,4,6-tetrakis (carboxyethyl) glycoluril, which is an intermediate for the production of the above 1,3,4,6-tetrakis (carboxyethyl) glycolurils, 4,6-Tetrakis (2-cyanoethyl) glycolurils are provided.
本発明による１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類は、分子中の４個の窒素原子上の水素原子がすべて、カルボキシルアルキル基で置換された新規な化合物、即ち、分子中に４個のカルボキシル基を有するグリコールウリル類である。 1,3,4,6-Tetrakis (carboxyalkyl) glycoluril according to the present invention is a novel compound in which all hydrogen atoms on four nitrogen atoms in a molecule are substituted with carboxylalkyl groups, ie, molecules Glycolurils having 4 carboxyl groups in them.
本発明によるこのような１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類は４官能性であるので、例えば、エポキシ樹脂の架橋剤として用いた場合、従来の２官能性や３官能性の架橋剤を用いた場合よりも、架橋密度のより高いエポキシ樹脂硬化物、従って、例えば、硬度、耐熱性、耐湿性等によりすぐれたエポキシ樹脂硬化物を得ることができる。 Since such 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention are tetrafunctional, for example, when used as a crosslinking agent for epoxy resins, conventional bifunctional or trifunctional It is possible to obtain an epoxy resin cured product having a higher crosslinking density, that is, an epoxy resin cured product having superior hardness, heat resistance, moisture resistance, etc.
また、本発明の方法によれば、上述した１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類を収率よく得ることができる。 In addition, according to the method of the present invention, the above-described 1,3,4,6-tetrakis (carboxyalkyl) glycoluril can be obtained with high yield.
本発明による１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類は一般式（Ｉ） The 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the invention are represented by the general formula (I)
（式中、ｎは０又は１を示し、Ｒ1及びＲ2はそれぞれ独立に水素原子又は低級アルキル基を示す。）
で表される。
(In the formula, n represents 0 or 1, and R 1 and R 2 each independently represent a hydrogen atom or a lower alkyl group.)
It is represented by
上記一般式（Ｉ）で表される１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類において、Ｒ1又はＲ2が低級アルキル基であるとき、その低級アルキル基は、通常、炭素原子数１〜５であり、好ましくは、１〜３であり、最も好ましくは１であり、従って、最も好ましい上記低級アルキル基はメチル基である。 In the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the above general formula (I), when R 1 or R 2 is a lower alkyl group, the lower alkyl group is usually carbon. It has 1 to 5 atoms, preferably 1 to 3, most preferably 1, and therefore the most preferred lower alkyl group is a methyl group.
従って、本発明による１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類の好ましい具体例として、例えば、
１，３，４，６−テトラキス（カルボキシルメチル）グリコールウリル、
１，３，４，６−テトラキス（２−カルボキシルエチル）グリコールウリル、
１，３，４，６−テトラキス（カルボキシルメチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（２−カルボキシルエチル）−３ａ−メチルグリコールウリル、
１，３，４，６−テトラキス（カルボキシルメチル）−３ａ，６ａ−ジメチルグリコールウリル、
１，３，４，６−テトラキス（２−カルボキシルエチル）−３ａ，６ａ−ジメチルグリコールウリル
等を挙げることができる。
Accordingly, preferred specific examples of 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention include, for example,
1,3,4,6-tetrakis (carboxylmethyl) glycoluril,
1,3,4,6-tetrakis (2-carboxylethyl) glycoluril,
1,3,4,6-tetrakis (carboxylmethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (2-carboxylethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (carboxylmethyl) -3a, 6a-dimethylglycoluril,
Examples include 1,3,4,6-tetrakis (2-carboxylethyl) -3a, 6a-dimethylglycoluril.
本発明による前記１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類のうち、ｎが０であるもの、即ち、下記一般式（II） Among the 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention, those in which n is 0, that is, the following general formula (II)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表される１，３，４，６−テトラキス（カルボキシメチル）グリコールウリル類は、次式に従って、一般式（ａ）
(In the formula, R 1 and R 2 are the same as described above.)
1,3,4,6-tetrakis (carboxymethyl) glycoluril represented by the general formula (a)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表されるジカルボニル化合物を、必要に応じて適宜の溶媒中、酸の存在下に一般式（ｂ）
(In the formula, R 1 and R 2 are the same as described above.)
The dicarbonyl compound represented by general formula (b) in the presence of an acid in an appropriate solvent as necessary.
（式中、Ｒ3は低級アルキル基を示す。）
で表される尿素誘導体（ｂ）と反応させることによって得ることができる。
(In the formula, R 3 represents a lower alkyl group.)
It can obtain by making it react with the urea derivative (b) represented by these.
上記尿素誘導体（ｂ）中のエステル基（−ＣＯ2Ｒ3）は、反応の際に加水分解されるエステル基であって、基Ｒ3は、好ましくは、炭素原子数１〜３のアルキル基であり、より好ましくは、メチル基又はエチル基である。従って、上記尿素誘導体（ｂ）としては、例えば、Ｎ，Ｎ’−カルボニルビス（グリシンメチル）やＮ，Ｎ’−カルボニルビス（グリシンエチル）が好ましく用いられる。 The ester group (—CO 2 R 3 ) in the urea derivative (b) is an ester group that is hydrolyzed during the reaction, and the group R 3 is preferably an alkyl group having 1 to 3 carbon atoms. And more preferably a methyl group or an ethyl group. Therefore, as the urea derivative (b), for example, N, N′-carbonylbis (glycinemethyl) and N, N′-carbonylbis (glycineethyl) are preferably used.
上記尿素誘導体（ｂ）は上記ジカルボニル化合物（ａ）１モル部に対して２〜１０モル部の割合にて、好ましくは、２〜４モル部の割合にて用いられる。 The urea derivative (b) is used in a proportion of 2 to 10 mol parts, preferably in a proportion of 2 to 4 mol parts, relative to 1 mol part of the dicarbonyl compound (a).
また、上記ジカルボニル化合物（ａ）としては、例えば、グリオキザール、２−オキソプロパナール、ジアセチル等が用いられる。 Examples of the dicarbonyl compound (a) include glyoxal, 2-oxopropanal, diacetyl and the like.
上記ジカルボニル化合物（ａ）と上記尿素誘導体（ｂ）の反応において用いられる酸としては、塩酸、硫酸等の無機酸や酢酸等の有機酸を挙げることができる。これら酸は、通常、ジカルボニル化合物（ａ）１モル部に対して、０．０５〜１０モル部の割合、好ましくは、０．１〜１．０モル部の割合で用いられる。 Examples of the acid used in the reaction of the dicarbonyl compound (a) and the urea derivative (b) include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. These acids are generally used in a proportion of 0.05 to 10 mol parts, preferably 0.1 to 1.0 mol parts, relative to 1 mol part of the dicarbonyl compound (a).
上記ジカルボニル化合物（ａ）と上記尿素誘導体（ｂ）の反応において、溶媒は、これを用いるときは、反応を阻害しない限りは、特に制限されることはないが、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のようなアルコール類、ヘキサン、ヘプタンのような脂肪族炭化水素類、アセトン、２−ブタノンのようなケトン類、酢酸エチル、酢酸ブチルのようなエステル類、ベンゼン、トルエン、キシレン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、Ｎ−メチルピロリジノン、ヘキサメチルホスホロトリアミドのようなアミド類、ジメチルスルホキシドのようなスルホキシド類等を挙げることができる。このような溶媒は単独で、又は２種以上を組み合わせて、適宜量が用いられる。 In the reaction of the dicarbonyl compound (a) and the urea derivative (b), the solvent is not particularly limited as long as it does not inhibit the reaction. For example, water, methanol, ethanol , Alcohols such as isopropyl alcohol, aliphatic hydrocarbons such as hexane and heptane, ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, benzene, toluene and xylene Aromatic hydrocarbons, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl Ethers such as ether, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, amides such as hexamethylphosphorotriamide, dimethylsulfoxide Such sulfoxides can be mentioned. These solvents are used alone or in combination of two or more, and an appropriate amount is used.
上記ジカルボニル化合物（ａ）と上記尿素誘導体（ｂ）の反応は、通常、−１０〜１５０℃の範囲の温度で行なわれ、好ましくは、０℃〜１００℃の範囲の温度で行なわれる。また、反応時間は、反応温度にもよるが、通常、１〜２４時間の範囲であり、好ましくは、１〜６時間の範囲である。 The reaction of the dicarbonyl compound (a) and the urea derivative (b) is usually performed at a temperature in the range of −10 to 150 ° C., preferably at a temperature in the range of 0 ° C. to 100 ° C. Moreover, although reaction time is based also on reaction temperature, it is the range of 1 to 24 hours normally, Preferably, it is the range of 1 to 6 hours.
上記ジカルボニル化合物（ａ）と上記尿素誘導体（ｂ）の反応の終了後、得られた反応混合物から、例えば、抽出等の操作によって、目的とする１，３，４，６−テトラキス（カルボキシメチル）グリコールウリル類を得ることができる。必要に応じて、更に、水等の溶媒による洗浄や活性炭処理等によって、目的とする１，３，４，６−テトラキス（カルボキシメチル）グリコールウリル類を精製することができる。 After completion of the reaction of the dicarbonyl compound (a) and the urea derivative (b), the desired 1,3,4,6-tetrakis (carboxymethyl) is obtained from the obtained reaction mixture by an operation such as extraction. ) Glycolurils can be obtained. If necessary, the desired 1,3,4,6-tetrakis (carboxymethyl) glycoluril can be further purified by washing with a solvent such as water or activated carbon treatment.
本発明による１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類のうち、ｎが１であるもの、即ち、下記一般式（III） Among the 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention, those in which n is 1, that is, the following general formula (III)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表される１，３，４，６−テトラキス（２−カルボキシエチル）グリコールウリル類は、一般式（ｃ）
(In the formula, R 1 and R 2 are the same as described above.)
1,3,4,6-tetrakis (2-carboxyethyl) glycoluril represented by the general formula (c)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表されるグリコールウリル類と、好ましくは適宜の溶媒中、塩基の存在下にアクリロニトリルを反応させて、一般式（ｄ）
(In the formula, R 1 and R 2 are the same as described above.)
Is reacted with acrylonitrile in the presence of a base, preferably in an appropriate solvent, to give a general formula (d)
（式中、Ｒ1及びＲ2は前記と同じである。）
で表される１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を得る第１工程、次いで、得られた１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を好ましくは適宜の溶媒中、酸の存在下に加水分解する第２工程を経ることによって得ることができる。
(In the formula, R 1 and R 2 are the same as described above.)
The first step of obtaining 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril represented by the following formula, then, the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is obtained. Preferably, it can be obtained by passing through a second step of hydrolysis in the presence of an acid in an appropriate solvent.
上記第１工程、即ち、グリコールウリル類（ｃ）とアクリロニトリルとの反応において、アクリロニトリルはグリコールウリル類（ｃ）１モル部に対して、通常、４．０〜２０．０モル部の割合にて、好ましくは、４．０〜８．０モル部の割合にて用いられる。 In the first step, that is, in the reaction of glycolurils (c) with acrylonitrile, acrylonitrile is usually in a ratio of 4.0 to 20.0 mol parts per mol part of glycolurils (c). Preferably, it is used in a proportion of 4.0 to 8.0 mole parts.
上記第１工程における塩基としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムｔｅｒｔ−ブトキシド等の無機塩基や、トリエチルアミン、ジイソプロピルエチルアミン、ＤＢＵ（１，８−ジアザビシクロ［５．４．０］ウンデ−７−セン）等の有機塩基が用いられる。これら塩基は、グリコールウリル類（ｃ）１モル部に対して、通常、０．０１〜５．０モル部の割合で用いられ、好ましくは、０．０１〜１．０モル部の割合で用いられる。 Examples of the base in the first step include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, triethylamine, diisopropylethylamine, DBU ( An organic base such as 1,8-diazabicyclo [5.4.0] unde-7-cene) is used. These bases are usually used in a proportion of 0.01 to 5.0 mol parts, preferably in a proportion of 0.01 to 1.0 mol parts, relative to 1 mol part of glycolurils (c). It is done.
また、上記第１工程において、溶媒は、これを用いるときは、反応を阻害しない限りは、特に、制限されることはないが、例えば、前記ジカルボニル化合物（ａ）と前記尿素誘導体（ｂ）の反応において用いる溶媒と同じ溶媒を用いることができる。 In the first step, when the solvent is used, it is not particularly limited as long as it does not inhibit the reaction. For example, the dicarbonyl compound (a) and the urea derivative (b) The same solvent as that used in the reaction can be used.
上記第１工程における反応温度と反応時間も、前記ジカルボニル化合物（ａ）と前記尿素誘導体（ｂ）の反応における反応温度と反応時間と同じである。 The reaction temperature and reaction time in the first step are also the same as the reaction temperature and reaction time in the reaction of the dicarbonyl compound (a) and the urea derivative (b).
上述した第１及び第２工程による１，３，４，６−テトラキス（カルボキシエチル）グリコールウリル類の合成に際しては、上記第１工程の終了後、得られた反応混合物から過剰のアクリロニトリルと溶媒を留去し、得られた残留物をそのまま、第２工程において、加水分解してもよいし、また、得られた１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を反応混合物から適宜手段にて分離して、これを第２工程において、加水分解に供してもよい。 In the synthesis of 1,3,4,6-tetrakis (carboxyethyl) glycoluril by the first and second steps described above, after completion of the first step, excess acrylonitrile and solvent are removed from the resulting reaction mixture. In the second step, the obtained residue may be hydrolyzed as it is, or the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is reacted with the reaction mixture. May be separated by appropriate means and subjected to hydrolysis in the second step.
上記第２工程、即ち、１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類の加水分解において用いられる酸としては、塩酸、硫酸等の無機酸や酢酸等の有機酸を挙げることができる。これら酸は、１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類１モル部に対して、通常、０．１〜２０．０モル部の割合にて、好ましくは、１．０〜３．０モル部の割合にて用いられる。 Examples of the acid used in the second step, that is, hydrolysis of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Can do. These acids are usually in a proportion of 0.1 to 20.0 mole parts, preferably 1.0 to 1 mole part of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril. Used at a ratio of ˜3.0 mole parts.
上記第２工程において用いられる溶媒は、反応を阻害しない限りは、特に、制限されることはないが、例えば、前記ジカルボニル化合物（ａ）と前記尿素誘導体（ｂ）の反応において用いる溶媒と同じ溶媒を用いることができる。 The solvent used in the second step is not particularly limited as long as the reaction is not inhibited. For example, the same solvent as used in the reaction of the dicarbonyl compound (a) and the urea derivative (b) is used. A solvent can be used.
また、上記１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類の加水分解の反応は、通常、０〜１５０℃の範囲の温度で行なわれ、好ましくは、室温乃至１００℃の範囲の温度で行なわれる。また、反応時間は、反応温度にもよるが、通常、１〜３６時間の範囲であり、好ましくは、１〜１６時間の範囲である。 The hydrolysis reaction of the 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is usually performed at a temperature in the range of 0 to 150 ° C., preferably in the range of room temperature to 100 ° C. At a temperature of Moreover, although reaction time is based also on reaction temperature, it is the range of 1 to 36 hours normally, Preferably, it is the range of 1 to 16 hours.
このようにして、上記１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類の加水分解反応の終了後、得られた反応混合物から、例えば、抽出等の操作によって、目的とする１，３，４，６−テトラキス（２−カルボキシエチル）グリコールウリル類を得ることができる。必要に応じて、更に、水等の溶媒による洗浄や活性炭処理等によって、目的とする１，３，４，６−テトラキス（２−カルボキシエチル）グリコールウリル類を精製することができる。 Thus, after completion | finish of the hydrolysis reaction of the said 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril, it is made into the target 1 by operation, such as extraction, from the obtained reaction mixture. , 3,4,6-tetrakis (2-carboxyethyl) glycoluril can be obtained. If necessary, the desired 1,3,4,6-tetrakis (2-carboxyethyl) glycoluril can be further purified by washing with a solvent such as water or activated carbon treatment.
本発明による１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類は、前述したように、分子中に４個のカルボキシル基を有し、従って、例えば、エポキシ樹脂のための架橋剤として有用である。 The 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention have four carboxyl groups in the molecule, as described above, and thus, for example, as crosslinkers for epoxy resins Useful.
本発明によるエポキシ樹脂組成物は、前記一般式（Ｉ）で表される１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類を架橋剤として含み、更に、アミン類からなる硬化剤を含む。 The epoxy resin composition according to the present invention contains 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (I) as a crosslinking agent, and further contains a curing agent composed of amines. Including.
本発明に従って、１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類を架橋剤として含むと共にアミン類からなる硬化剤を含むエポキシ樹脂組成物は、従来、知られているエポキシ樹脂組成物に比べて、架橋密度のより高いエポキシ樹脂硬化物、従って、例えば、硬度、耐熱性、耐湿性等によりすぐれたエポキシ樹脂硬化物を与える。 In accordance with the present invention, an epoxy resin composition comprising 1,3,4,6-tetrakis (carboxyalkyl) glycoluril as a crosslinking agent and a curing agent comprising an amine is a conventionally known epoxy resin composition. In comparison with the above, a cured epoxy resin having a higher crosslink density, and therefore, an cured epoxy resin superior in hardness, heat resistance, moisture resistance, etc., for example, is provided.
本発明において、上記エポキシ樹脂とは、平均して１分子当り２個以上のエポキシ基を有するエポキシ化合物をいい、従って、よく知られているように、そのようなエポキシ樹脂として、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、カテコール、レゾルシノール等の多価フェノール、グリセリンやポリエチレングリコール等の多価アルコールとエピクロルヒドリンを反応させて得られるポリグリシジルエーテル類、ｐ−ヒドロキシ安息香酸、β−ヒドロキシナフトエ酸のようなヒドロキシカルボン酸とエピクロルヒドリンを反応させて得られるグリシジルエーテルエステル類、フタル酸、テレフタル酸のようなポリカルボン酸とエピクロルヒドリンを反応させて得られるポリグリシジルエステル類、更に、エポキシ化フェノールノボラック樹脂、エポキシ化クレゾールノボラック樹脂、エポキシ化ポリオレフィン、環式脂肪族エポキシ樹脂、ウレタン変性エポキシ樹脂等を挙げることができるが、しかし、本発明において、エポキシ樹脂は上記例示に限定されるものではない。 In the present invention, the above-mentioned epoxy resin means an epoxy compound having two or more epoxy groups per molecule on average. Therefore, as is well known, as such an epoxy resin, for example, bisphenol A is used. Polyglycidyl ethers obtained by reacting polychlorophenols such as bisphenol F, bisphenol AD, catechol and resorcinol, polyhydric alcohols such as glycerin and polyethylene glycol and epichlorohydrin, p-hydroxybenzoic acid, β-hydroxynaphthoic acid Glycidyl ether esters obtained by reacting such a hydroxycarboxylic acid with epichlorohydrin, polyglycidyl esters obtained by reacting a polycarboxylic acid such as phthalic acid or terephthalic acid with epichlorohydrin, and epoxy Phenol novolac resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin, urethane-modified epoxy resin, and the like can be mentioned. However, in the present invention, the epoxy resin is not limited to the above examples. Absent.
本発明によるエポキシ樹脂組成物におけるアミン類からなる硬化剤としては、従来から知られているように、エポキシ基と付加反応し得る活性水素を分子内に１個以上有すると共に、１級アミノ基、２級アミノ基及び３級アミノ基から選ばれるアミノ基を分子内に少なくとも１個有するものであればよい。このようなアミン類からなる硬化剤として、例えば、ジエチレントリアミン、トリエチレンテトラミン、ｎ−プロピルアミン、２−ヒドロキシエチルアミノプロピルアミン、シクロヘキシルアミン、４，４′−ジアミノジシクロヘキシルメタンのような脂肪族アミン類、４，４′−ジアミノジフェニルメタン、２−メチルアニリン等の芳香族アミン類、２−エチル−４−メチルイミダゾール、２−メチルイミダゾール、２−エチル−４−メチルイミダゾリン、２，４−ジメチルイミダゾリン、ピペリジン、ピペラジンのような窒素含有複素環化合物等を挙げることができる。しかし、本発明において、アミン類からなる硬化剤は上記例示に限定されるものではない。 As known in the art, the curing agent comprising amines in the epoxy resin composition according to the present invention has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule, and a primary amino group, What is necessary is just to have at least one amino group selected from a secondary amino group and a tertiary amino group in the molecule. Examples of the curing agent comprising such amines include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diaminodicyclohexylmethane. 4,4′-diaminodiphenylmethane, aromatic amines such as 2-methylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, Examples thereof include nitrogen-containing heterocyclic compounds such as piperidine and piperazine. However, in this invention, the hardening | curing agent which consists of amines is not limited to the said illustration.
更に、本発明によるエポキシ樹脂組成物は、必要に応じて、充填剤、希釈剤、溶剤、顔料、可撓性付与剤、カップリング剤、酸化防止剤等、種々の添加剤を含んでいてもよい。 Furthermore, the epoxy resin composition according to the present invention may contain various additives such as a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, and an antioxidant as necessary. Good.
以下に本発明を実施例によって説明するが、本発明はそれら実施例によって特に限定されるものではない。 The present invention will be described below with reference to examples, but the present invention is not particularly limited to these examples.
尚、以下において、Ｎ，Ｎ’−カルボニルビス（グリシンメチル）は、Ｓｙｎｌｅｔｔ、第７巻、第１１０４〜１１０６頁（２０１０年）に記載された方法に従って合成したものを用いた。 In the following, N, N′-carbonylbis (glycinemethyl) was synthesized according to the method described in Synlett, Vol. 7, pages 1104 to 1106 (2010).
また、４０％グリオキザール水溶液、グリコールウリル及びアクリロニトリルはいずれも東京化成工業（株）製を用い、ＤＢＵは和光純薬工業（株）製を用いた。 Further, 40% aqueous glyoxal solution, glycoluril and acrylonitrile were all manufactured by Tokyo Chemical Industry Co., Ltd., and DBU was manufactured by Wako Pure Chemical Industries, Ltd.
実施例１
（１，３，４，６−テトラキス（カルボキシルメチル）グリコールウリルの合成）
温度計を備えた１００ｍＬフラスコにＮ，Ｎ’−カルボニルビス（グリシンメチル）２．０４ｇ（１０．０ｍｍｏｌ）、４０％グリオキザール水溶液７２６ｍｇ（５．０ｍｍｏｌ）、酢酸１０ｍＬ及び硫酸４９ｍｇ（０．５ｍｍｏｌ）を投入した。
Example 1
(Synthesis of 1,3,4,6-tetrakis (carboxylmethyl) glycoluril)
A 100 mL flask equipped with a thermometer was charged with 2.04 g (10.0 mmol) of N, N′-carbonylbis (glycine methyl), 726 mg (5.0 mmol) of 40% aqueous glyoxal solution, 10 mL of acetic acid and 49 mg (0.5 mmol) of sulfuric acid. I put it in.
得られた混合物を１１０℃にて終夜攪拌した後、室温まで冷却し、アセトン５０ｍＬを加え、析出した結晶を濾別し、乾燥して、１，３，４，６−テトラキス（カルボキシルメチル）グリコールウリル１．２６ｇを白色結晶として得た。収率６７％。 The resulting mixture was stirred at 110 ° C. overnight, cooled to room temperature, 50 mL of acetone was added, the precipitated crystals were filtered off, dried, and dried with 1,3,4,6-tetrakis (carboxylmethyl) glycol. 1.26 g of uril was obtained as white crystals. Yield 67%.
得られた１，３，４，６−テトラキス（カルボキシルメチル）グリコールウリルは融点２２３〜２３９℃であった。そのＩＲスペクトルを図１に示す。また、その１Ｈ−ＮＭＲスペクトル（ｄ６−ＤＭＳＯ）におけるδ値は下記のとおりであった。 The obtained 1,3,4,6-tetrakis (carboxylmethyl) glycoluril had a melting point of 223 to 239 ° C. The IR spectrum is shown in FIG. Further, the δ value in the 1 H-NMR spectrum (d6-DMSO) was as follows.
１２．８（ｂｒ，４Ｈ），５．５２（ｓ，２Ｈ），４．０５（ｄ，４Ｈ），３．８５（ｄ，４Ｈ） 12.8 (br, 4H), 5.52 (s, 2H), 4.05 (d, 4H), 3.85 (d, 4H)
実施例２
（１，３，４，６−テトラキス（２−シアノエチル）グリコールウリルの合成）
温度計を備えた２００ｍＬオートクレーブ容器にグリコールウリル１３．５４ｇ（９５．３ｍｍｏｌ）、アクリロニトリル３５．３８ｇ（６６６．８ｍｍｏｌ）、ＤＢＵ０．５８ｇ（３．８ｍｍｏｌ）及び水５４ｍＬを投入した。
Example 2
(Synthesis of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril)
A 200 mL autoclave vessel equipped with a thermometer was charged with 13.54 g (95.3 mmol) of glycoluril, 35.38 g (666.8 mmol) of acrylonitrile, 0.58 g (3.8 mmol) of DBU and 54 mL of water.
得られた混合物を１２０℃にて５時間攪拌した後、室温まで冷却した。析出した結晶を濾別し、アセトン５０ｍＬ／水１０ｍＬの混合溶媒から再結晶して、１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル２０．７５ｇを白色結晶として得た。収率６１％。 The resulting mixture was stirred at 120 ° C. for 5 hours and then cooled to room temperature. The precipitated crystals were separated by filtration and recrystallized from a mixed solvent of 50 mL of acetone / 10 mL of water to obtain 20.75 g of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril as white crystals. Yield 61%.
得られた１，３，４，６−テトラキス（２−シアノエチル）グリコールウリルの融点は１３９〜１４１℃であった。そのＩＲスペクトルを図２に示す。また、その１Ｈ−ＮＭＲスペクトル（ｄ６−ＤＭＳＯ）におけるδ値は下記のとおりであった。 The melting point of the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril was 139 to 141 ° C. The IR spectrum is shown in FIG. Further, the δ value in the 1 H-NMR spectrum (d6-DMSO) was as follows.
５．５０（ｓ，２Ｈ），３．６４−３．７１（ｍ，４Ｈ），３．４４−３．５１（ｍ，４Ｈ），２．７９（ｔ，８Ｈ） 5.50 (s, 2H), 3.64-3.71 (m, 4H), 3.44-3.51 (m, 4H), 2.79 (t, 8H)
実施例３
（１，３，４，６−テトラキス（２−カルボキシルエチル）グリコールウリルの合成）
温度計を備えた１００ｍＬフラスコに１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル１０．００ｇ（２８．２ｍｍｏｌ）と濃塩酸２０ｍＬを投入した。
Example 3
(Synthesis of 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril)
A 100 mL flask equipped with a thermometer was charged with 10.00 g (28.2 mmol) of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril and 20 mL of concentrated hydrochloric acid.
得られた混合物を１１０℃にて２時間攪拌した後、減圧下で濃縮し、得られた濃縮物にアセトン４０ｍＬを投入した。不溶物を濾過によって除去した後、濾液を氷冷下に１時間攪拌した。析出した結晶を濾別し、乾燥して、１，３，４，６−テトラキス（２−カルボキシルエチル）グリコールウリル４．６２ｇを白色結晶として得た。収率３８％。 The resulting mixture was stirred at 110 ° C. for 2 hours, then concentrated under reduced pressure, and 40 mL of acetone was added to the resulting concentrate. The insoluble material was removed by filtration, and the filtrate was stirred for 1 hour under ice cooling. The precipitated crystals were separated by filtration and dried to obtain 4.62 g of 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril as white crystals. Yield 38%.
得られた１，３，４，６−テトラキス（２−カルボキシルエチル）グリコールウリルの融点は１１５〜１２１℃であった。そのＩＲスペクトルを図３に示す。また、その１Ｈ−ＮＭＲスペクトル（Ｄ2Ｏ）におけるδ値は下記のとおりであった。 The melting point of the obtained 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril was 115 to 121 ° C. The IR spectrum is shown in FIG. Further, the δ value in the 1 H-NMR spectrum (D 2 O) was as follows.
３．９９（ｓ，２Ｈ），３．８８（ｔ，２Ｈ），３．６６（ｔ，２Ｈ），３．５７（ｔ，２Ｈ），３．２７（ｔ，２Ｈ），２．６４（ｔ，２Ｈ），２．５８（ｔ，４Ｈ），２．０５（ｔ，２Ｈ） 3.99 (s, 2H), 3.88 (t, 2H), 3.66 (t, 2H), 3.57 (t, 2H), 3.27 (t, 2H), 2.64 (t , 2H), 2.58 (t, 4H), 2.05 (t, 2H)
本発明による１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類は、４個の窒素原子を環構造中に有するヘテロ環からなり、それぞれの窒素原子上の水素原子がいずれもカルボキシルアルキル基で置換された新規な化合物、即ち、分子中に４個のカルボキシル基を有する化合物である。 The 1,3,4,6-tetrakis (carboxyalkyl) glycoluril according to the present invention consists of a heterocycle having four nitrogen atoms in the ring structure, and any hydrogen atom on each nitrogen atom is a carboxyalkyl. A novel compound substituted with a group, that is, a compound having four carboxyl groups in the molecule.
従って、このような化合物は、例えば、エポキシ樹脂の架橋剤や半田フラックス活性剤として有用である。
Accordingly, such a compound is useful, for example, as an epoxy resin crosslinking agent or a solder flux activator.
Claims (6)
で表される１，３，４，６−テトラキス（カルボキシアルキル）グリコールウリル類。 Formula (I)
1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by
で表されるジカルボニル化合物と一般式（ｂ）
で表される尿素誘導体（ｂ）を反応させることを含む一般式（II）
で表される１，３，４，６−テトラキス（カルボキシメチル）グリコールウリル類の製造方法。 In the presence or absence of a solvent, in the presence of an acid, the general formula (a)
And a general formula (b)
Which comprises reacting a urea derivative (b) represented by the general formula (II)
The manufacturing method of 1,3,4,6-tetrakis (carboxymethyl) glycoluril represented by these.
で表されるグリコールウリル類とアクリロニトリルを反応させて、一般式（ｄ）
で表される１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を得る第１工程、次いで、溶媒の存在下又は不存在下、酸の存在下に、上記１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類を加水分解する第２工程を含む一般式（III）
で表される１，３，４，６−テトラキス（カルボキシエチル）グリコールウリル類の製造方法。 In the presence or absence of a solvent, in the presence of a base, the general formula (c)
Is reacted with acrylonitrile represented by the general formula (d)
In the first step of obtaining 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril represented by the following, then in the presence or absence of a solvent, in the presence of an acid, the above 1,3,4 , 6-Tetrakis (2-cyanoethyl) glycoluril having the second step of hydrolyzing the general formula (III)
The manufacturing method of 1,3,4,6-tetrakis (carboxyethyl) glycoluril represented by these.
で表される１，３，４，６−テトラキス（２−シアノエチル）グリコールウリル類。
General formula (d)
1,3,4,6-tetrakis (2-cyanoethyl) glycoluril represented by the formula:
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| JP2016222546A (en) * | 2015-05-27 | 2016-12-28 | 日本化薬株式会社 | Polycarboxylic acid, polycarboxylic acid composition comprising the same, and epoxy resin composition |
| JP2017066076A (en) * | 2015-09-30 | 2017-04-06 | 四国化成工業株式会社 | 1,3,4,6-tetrakis (aminoalkyl) glycoluril compound, synthesis method and epoxy resin curing agent |
| CN115808847A (en) * | 2023-01-18 | 2023-03-17 | 苏州润邦半导体材料科技有限公司 | Anti-reflection coating resin at bottom of photoresist as well as preparation method and application thereof |
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| CN115808847A (en) * | 2023-01-18 | 2023-03-17 | 苏州润邦半导体材料科技有限公司 | Anti-reflection coating resin at bottom of photoresist as well as preparation method and application thereof |
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