JP2008174520A - Sulfur-containing polyisocyanate compound - Google Patents
Sulfur-containing polyisocyanate compound Download PDFInfo
- Publication number
- JP2008174520A JP2008174520A JP2007011381A JP2007011381A JP2008174520A JP 2008174520 A JP2008174520 A JP 2008174520A JP 2007011381 A JP2007011381 A JP 2007011381A JP 2007011381 A JP2007011381 A JP 2007011381A JP 2008174520 A JP2008174520 A JP 2008174520A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- integer
- bis
- polyisocyanate compound
- 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
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 36
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 6
- 229910052717 sulfur Inorganic materials 0.000 title description 6
- 239000011593 sulfur Substances 0.000 title description 6
- -1 silyl halide Chemical class 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000006462 rearrangement reaction Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000006969 Curtius rearrangement reaction Methods 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- LORRLQMLLQLPSJ-UHFFFAOYSA-N 1,3,5-trithiane Chemical group C1SCSCS1 LORRLQMLLQLPSJ-UHFFFAOYSA-N 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- NLGXAVLTHLSJPO-UHFFFAOYSA-N N(=C=O)CC1SCSC(S1)CN=C=O Chemical compound N(=C=O)CC1SCSC(S1)CN=C=O NLGXAVLTHLSJPO-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006295 polythiol Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HCZVKPXJTQGYEC-UHFFFAOYSA-N CC(=O)SC(CNC(=O)OC)OC Chemical compound CC(=O)SC(CNC(=O)OC)OC HCZVKPXJTQGYEC-UHFFFAOYSA-N 0.000 description 3
- WPFQUAFRIKYYQO-UHFFFAOYSA-N COC(=O)CC1SCSC(S1)CC(=O)OC Chemical compound COC(=O)CC1SCSC(S1)CC(=O)OC WPFQUAFRIKYYQO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-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
- QNSUVMHSJGIMDL-UHFFFAOYSA-N [6-(sulfanylmethylsulfanyl)-1,3-dithian-4-yl]sulfanylmethanethiol Chemical compound SCSC1CC(SCS)SCS1 QNSUVMHSJGIMDL-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000582 polyisocyanurate Polymers 0.000 description 3
- 239000011495 polyisocyanurate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 0 *C(*)C1(CC2)CC2(*)CC1 Chemical compound *C(*)C1(CC2)CC2(*)CC1 0.000 description 2
- FDJWTMYNYYJBAT-UHFFFAOYSA-N 1,3,3-tris(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSC(SCS)CC(SCS)SCS FDJWTMYNYYJBAT-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- IMLSAISZLJGWPP-UHFFFAOYSA-N 1,3-dithiolane Chemical group C1CSCS1 IMLSAISZLJGWPP-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- GYSJZHBZFVDFIT-UHFFFAOYSA-N COC(CNC(=O)OC)S Chemical compound COC(CNC(=O)OC)S GYSJZHBZFVDFIT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NITQFNYRKUAWHQ-UHFFFAOYSA-N [2-(1,3-dithietan-2-yl)-1-(sulfanylmethylsulfanyl)ethyl]sulfanylmethanethiol Chemical compound SCSC(SCS)CC1SCS1 NITQFNYRKUAWHQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N carbamic acid methyl ester Natural products COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical class N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical group SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XVNGTGZGWDPIRR-UHFFFAOYSA-N 1,2,2-tris(sulfanylmethylsulfanyl)ethylsulfanylmethanethiol Chemical compound SCSC(SCS)C(SCS)SCS XVNGTGZGWDPIRR-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 description 1
- FEWPLEANLZQRRE-UHFFFAOYSA-N 1,3-bis(4-chlorophenyl)propane-2,2-dithiol Chemical compound C=1C=C(Cl)C=CC=1CC(S)(S)CC1=CC=C(Cl)C=C1 FEWPLEANLZQRRE-UHFFFAOYSA-N 0.000 description 1
- CNAIYFIVNYOUFM-UHFFFAOYSA-N 1,3-bis(4-methoxyphenyl)propane-2,2-dithiol Chemical compound C1=CC(OC)=CC=C1CC(S)(S)CC1=CC=C(OC)C=C1 CNAIYFIVNYOUFM-UHFFFAOYSA-N 0.000 description 1
- KADZDOLYFZTSSM-UHFFFAOYSA-N 1,3-diphenylpropane-2,2-dithiol Chemical compound C=1C=CC=CC=1CC(S)(S)CC1=CC=CC=C1 KADZDOLYFZTSSM-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- CPWFHLLBKVXEBO-UHFFFAOYSA-N 1-isocyanato-3-(3-isocyanatopropylsulfanyl)propane Chemical compound O=C=NCCCSCCCN=C=O CPWFHLLBKVXEBO-UHFFFAOYSA-N 0.000 description 1
- JEARXBADBBQFGS-UHFFFAOYSA-N 1-methoxypropane-1,2-dithiol Chemical compound COC(S)C(C)S JEARXBADBBQFGS-UHFFFAOYSA-N 0.000 description 1
- DLLOHKQWGFKFLO-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dithiol Chemical compound CC1(S)CCCCC1S DLLOHKQWGFKFLO-UHFFFAOYSA-N 0.000 description 1
- MTZVWTOVHGKLOX-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)(CS)CS MTZVWTOVHGKLOX-UHFFFAOYSA-N 0.000 description 1
- MLHBQCMRBXCFLT-UHFFFAOYSA-N 2,2-bis(sulfanylmethylsulfanyl)ethanethiol Chemical compound SCSC(CS)SCS MLHBQCMRBXCFLT-UHFFFAOYSA-N 0.000 description 1
- VAAWBNFNCBSMQF-UHFFFAOYSA-N 2,2-bis(sulfanylmethylsulfanyl)ethylsulfanylmethanethiol Chemical compound SCSCC(SCS)SCS VAAWBNFNCBSMQF-UHFFFAOYSA-N 0.000 description 1
- ZNYYTLZIYMQBAF-UHFFFAOYSA-N 2,2-bis(sulfanylmethylsulfanyl)propane-1,3-dithiol Chemical compound SCSC(CS)(CS)SCS ZNYYTLZIYMQBAF-UHFFFAOYSA-N 0.000 description 1
- QKWWDTYDYOFRJL-UHFFFAOYSA-N 2,2-dimethoxyethanamine Chemical compound COC(CN)OC QKWWDTYDYOFRJL-UHFFFAOYSA-N 0.000 description 1
- SGLYOTGYKDFSSC-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-dithiol Chemical compound SCC(C)(C)CS SGLYOTGYKDFSSC-UHFFFAOYSA-N 0.000 description 1
- VROVQUCZZBDADS-UHFFFAOYSA-N 2,3-bis(3-sulfanylpropanoyloxy)propyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(OC(=O)CCS)COC(=O)CCS VROVQUCZZBDADS-UHFFFAOYSA-N 0.000 description 1
- FQZMBPXSKSSKCP-UHFFFAOYSA-N 2,3-bis(sulfanyl)propyl 2-sulfanylacetate Chemical compound SCC(S)COC(=O)CS FQZMBPXSKSSKCP-UHFFFAOYSA-N 0.000 description 1
- DGPOVPJSXNLHJO-UHFFFAOYSA-N 2,3-bis(sulfanyl)propyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(S)CS DGPOVPJSXNLHJO-UHFFFAOYSA-N 0.000 description 1
- VSKAJYQVWVOVRT-UHFFFAOYSA-N 2,3-bis[(2-sulfanylacetyl)oxy]propyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(OC(=O)CS)COC(=O)CS VSKAJYQVWVOVRT-UHFFFAOYSA-N 0.000 description 1
- JSGLUMKISYZQHM-UHFFFAOYSA-N 2,4-dimethylbenzene-1,3-dithiol Chemical compound CC1=CC=C(S)C(C)=C1S JSGLUMKISYZQHM-UHFFFAOYSA-N 0.000 description 1
- YRHRHYSCLREHLE-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)-1,4-dithiane Chemical compound O=C=NCC1CSC(CN=C=O)CS1 YRHRHYSCLREHLE-UHFFFAOYSA-N 0.000 description 1
- BDLJDZLEOKUVHM-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)thiophene Chemical compound O=C=NCC1=CC=C(CN=C=O)S1 BDLJDZLEOKUVHM-UHFFFAOYSA-N 0.000 description 1
- XAYMPCGHLKVJSR-UHFFFAOYSA-N 2,5-dichlorobenzene-1,3-dithiol Chemical compound SC1=CC(Cl)=CC(S)=C1Cl XAYMPCGHLKVJSR-UHFFFAOYSA-N 0.000 description 1
- JNVYHRRERQYAEF-UHFFFAOYSA-N 2,5-diisocyanato-1,4-dithiane Chemical compound O=C=NC1CSC(N=C=O)CS1 JNVYHRRERQYAEF-UHFFFAOYSA-N 0.000 description 1
- QNKIKONDIUVILW-UHFFFAOYSA-N 2,5-diisocyanatothiophene Chemical compound O=C=NC1=CC=C(N=C=O)S1 QNKIKONDIUVILW-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- UXUPVPJMGKWUSY-UHFFFAOYSA-N 2-(2-sulfanylphenyl)benzenethiol Chemical group SC1=CC=CC=C1C1=CC=CC=C1S UXUPVPJMGKWUSY-UHFFFAOYSA-N 0.000 description 1
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 1
- WDZGTNIUZZMDIA-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.OCC(C)(CO)CO WDZGTNIUZZMDIA-UHFFFAOYSA-N 0.000 description 1
- WFUMVIYEGASPLY-UHFFFAOYSA-N 2-[2,3,4-tris(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C(CCS)=C1CCS WFUMVIYEGASPLY-UHFFFAOYSA-N 0.000 description 1
- YZIGUJRGKPNSGI-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC(CCS)=C1CCS YZIGUJRGKPNSGI-UHFFFAOYSA-N 0.000 description 1
- XZJYDCHXNLYCTQ-UHFFFAOYSA-N 2-[2,4,5-tris(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=C(CCS)C=C1CCS XZJYDCHXNLYCTQ-UHFFFAOYSA-N 0.000 description 1
- ISGHUYCZFWLBRU-UHFFFAOYSA-N 2-[2-(2-sulfanylacetyl)oxyethoxy]ethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOCCOC(=O)CS ISGHUYCZFWLBRU-UHFFFAOYSA-N 0.000 description 1
- HVVRGPYMAUJRKF-UHFFFAOYSA-N 2-[2-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC=C1CCS HVVRGPYMAUJRKF-UHFFFAOYSA-N 0.000 description 1
- ZQLHFUHXRDOCBC-UHFFFAOYSA-N 2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOC(=O)CCS ZQLHFUHXRDOCBC-UHFFFAOYSA-N 0.000 description 1
- ZVWSJLHJHVTNCA-UHFFFAOYSA-N 2-[3,4,5-tris(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=C(CCS)C(CCS)=C1 ZVWSJLHJHVTNCA-UHFFFAOYSA-N 0.000 description 1
- YIMJMXYFLBUNMH-UHFFFAOYSA-N 2-[3,4-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C(CCS)=C1 YIMJMXYFLBUNMH-UHFFFAOYSA-N 0.000 description 1
- GFSULDUIAFNGRB-UHFFFAOYSA-N 2-[3,5-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=CC(CCS)=C1 GFSULDUIAFNGRB-UHFFFAOYSA-N 0.000 description 1
- RKPZXQVJXKNNSB-UHFFFAOYSA-N 2-[3-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC(CCS)=C1 RKPZXQVJXKNNSB-UHFFFAOYSA-N 0.000 description 1
- PESHQGQMMIRLMA-UHFFFAOYSA-N 2-[4-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C=C1 PESHQGQMMIRLMA-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 1
- VWJQYGOMEPVJRD-UHFFFAOYSA-N 3,3-bis(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSCCC(SCS)SCS VWJQYGOMEPVJRD-UHFFFAOYSA-N 0.000 description 1
- TVLKIWFNAPTXLZ-UHFFFAOYSA-N 3,4-bis(isocyanatomethyl)thiolane Chemical compound O=C=NCC1CSCC1CN=C=O TVLKIWFNAPTXLZ-UHFFFAOYSA-N 0.000 description 1
- KOCAIQHVJFBWHC-UHFFFAOYSA-N 3,4-dimethoxybutane-1,2-dithiol Chemical compound COCC(OC)C(S)CS KOCAIQHVJFBWHC-UHFFFAOYSA-N 0.000 description 1
- FIRKZKJPVSZLOZ-UHFFFAOYSA-N 3-(1,3-dithiolan-2-ylmethylsulfanyl)propane-1,2-dithiol Chemical compound SCC(S)CSCC1SCCS1 FIRKZKJPVSZLOZ-UHFFFAOYSA-N 0.000 description 1
- QDNHFLDYNJTWKV-UHFFFAOYSA-N 3-methoxypropane-1,2-dithiol Chemical compound COCC(S)CS QDNHFLDYNJTWKV-UHFFFAOYSA-N 0.000 description 1
- CWNPOQFCIIFQDM-UHFFFAOYSA-N 3-nitrobenzyl alcohol Chemical compound OCC1=CC=CC([N+]([O-])=O)=C1 CWNPOQFCIIFQDM-UHFFFAOYSA-N 0.000 description 1
- KZPQYIBJZXONAE-UHFFFAOYSA-N 4,5-bis(isocyanatomethyl)-1,3-dithiolane Chemical compound O=C=NCC1SCSC1CN=C=O KZPQYIBJZXONAE-UHFFFAOYSA-N 0.000 description 1
- CUVNZIBIDCGPQO-UHFFFAOYSA-N 4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane Chemical compound CC1SC(CN=C=O)C(CN=C=O)S1 CUVNZIBIDCGPQO-UHFFFAOYSA-N 0.000 description 1
- OOTLTOXPCLYKTL-UHFFFAOYSA-N 4,5-diisocyanato-1,3-dithiolane Chemical compound O=C=NC1SCSC1N=C=O OOTLTOXPCLYKTL-UHFFFAOYSA-N 0.000 description 1
- IMBFPOUWDJSNDI-UHFFFAOYSA-N 4,5-dimethylbenzene-1,3-dithiol Chemical compound CC1=CC(S)=CC(S)=C1C IMBFPOUWDJSNDI-UHFFFAOYSA-N 0.000 description 1
- ROCVXEQKCOWTAG-UHFFFAOYSA-N 4-[2-(4-sulfanylphenyl)ethyl]benzenethiol Chemical group C1=CC(S)=CC=C1CCC1=CC=C(S)C=C1 ROCVXEQKCOWTAG-UHFFFAOYSA-N 0.000 description 1
- FOWDDWLRTIXWET-UHFFFAOYSA-N 4-[4-(4-sulfanylphenyl)pentan-2-yl]benzenethiol Chemical compound C=1C=C(S)C=CC=1C(C)CC(C)C1=CC=C(S)C=C1 FOWDDWLRTIXWET-UHFFFAOYSA-N 0.000 description 1
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 description 1
- LKTVLEWRIFAXPR-UHFFFAOYSA-N CC(C(C)S)S.C(CCCS)S Chemical compound CC(C(C)S)S.C(CCCS)S LKTVLEWRIFAXPR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- FNTKCWQKAGGZFV-UHFFFAOYSA-N [2,3,4-tris(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C(CS)=C1CS FNTKCWQKAGGZFV-UHFFFAOYSA-N 0.000 description 1
- SDEFSQDZLUZWPW-UHFFFAOYSA-N [2,3-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1CS SDEFSQDZLUZWPW-UHFFFAOYSA-N 0.000 description 1
- LJODQQVXMSKBHT-UHFFFAOYSA-N [2,4,5-tris(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC(CS)=C(CS)C=C1CS LJODQQVXMSKBHT-UHFFFAOYSA-N 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- 230000008025 crystallization Effects 0.000 description 1
- VSARMWHOISBCGR-UHFFFAOYSA-N cyclohexane-1,1-dithiol Chemical compound SC1(S)CCCCC1 VSARMWHOISBCGR-UHFFFAOYSA-N 0.000 description 1
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- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- HYRAFPWOUAMMQN-UHFFFAOYSA-N naphthalene-1,4-dithiol Chemical compound C1=CC=C2C(S)=CC=C(S)C2=C1 HYRAFPWOUAMMQN-UHFFFAOYSA-N 0.000 description 1
- AAPAGLBSROJFGM-UHFFFAOYSA-N naphthalene-1,5-dithiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1S AAPAGLBSROJFGM-UHFFFAOYSA-N 0.000 description 1
- XMHBJPKFTZSWRJ-UHFFFAOYSA-N naphthalene-2,6-dithiol Chemical compound C1=C(S)C=CC2=CC(S)=CC=C21 XMHBJPKFTZSWRJ-UHFFFAOYSA-N 0.000 description 1
- INUVVGTZMFIDJF-UHFFFAOYSA-N naphthalene-2,7-dithiol Chemical compound C1=CC(S)=CC2=CC(S)=CC=C21 INUVVGTZMFIDJF-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、新規な含硫ポリイソシアナート化合物と新規な含硫ポリイソシアナート化合物の重合物および重合物からなる光学製品に関するものである。 The present invention relates to a novel sulfur-containing polyisocyanate compound, a polymer of the novel sulfur-containing polyisocyanate compound, and an optical product comprising the polymer.
プラスチックレンズは、無機レンズに比べ軽量で割れ難く、染色が可能なため近年、眼鏡レンズ、カメラレンズ等の光学素子に急速に普及してきている。
プラスチックレンズ用樹脂には、さらなる高性能化が要求されてきており、例えば高屈折率化、高アッベ数化、低比重化、高耐熱性化等が求められてきた。これまでにも様々なレンズ用樹脂素材が開発され使用されている。
その中でも、ポリウレタン系樹脂に関する提案が盛んに行われている(特許文献1、特許文献2、及び特許文献3)。
これらのポリチオールとポリイソ(チオ)シアナート化合物等とを反応させて得られる樹脂は、高屈折率低分散であり、衝撃性、染色性、加工性等に優れたプラスチックレンズに最適な樹脂の一つであり広く世の中に普及している。
In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.
The plastic lens resin has been required to have higher performance, for example, higher refractive index, higher Abbe number, lower specific gravity, higher heat resistance, and the like. Various resin materials for lenses have been developed and used so far.
Among them, proposals regarding polyurethane-based resins have been actively made (Patent Document 1, Patent Document 2, and Patent Document 3).
Resins obtained by reacting these polythiols with polyiso (thio) cyanate compounds, etc. are one of the most suitable resins for plastic lenses with high refractive index and low dispersion and excellent impact, dyeability, and processability. It is widespread in the world.
上記に示すようなポリチオールとポリイソ(チオ)シアナート化合物の更なる改良の方向性として、樹脂組成物中の高屈折率な原子である硫黄の含量を増加させ、さらに高屈折率の樹脂を得ようとする試みがなされている。例えば、高硫黄含量のポリイソ(チオ)シアナート化合物として、1,3−ジチオラン骨格を有するポリイソシアナート化合物とポリチオール化合物との重合により、定分散かつ高屈折率な優れた樹脂が得られることが知られている(特許文献4、特許文献5)。このような試みの中で、1,3−ジチオラン骨格と同様に硫黄含量の高い骨格である1,3,5−トリチアン骨格を有するポリイソシアナート化合物についてはこれまで報告例はなかった
従来合成されることの無かった1,3,5−トリチアン骨格を有するポリイソシアナート化合物の合成法を開発して、高屈折率樹脂の材料となる新規な1,3,5−トリチアン骨格を有するポリイソシアナート化合物を供給する。 Developed a method for synthesizing polyisocyanate compounds having a 1,3,5-trithiane skeleton, which has never been synthesized, and has a novel 1,3,5-trithiane skeleton that can be used as a material for high refractive index resins A polyisocyanate compound is supplied.
本発明者らは前記課題について鋭意検討を行った結果、任意の置換基を導入した環化前駆体からトリチアン骨格構築法とそれらのポリイソシアネート化合物へ変換法を開発し、新規な1,3,5−トリチアン骨格を有するポリイソシアナート化合物の合成に成功した。
すなわち、本発明は、
[1]
式(1)
As a result of intensive studies on the above problems, the present inventors have developed a method for constructing a trithian skeleton from a cyclized precursor introduced with an arbitrary substituent and a method for converting them into a polyisocyanate compound. A polyisocyanate compound having a 5-trithian skeleton was successfully synthesized.
That is, the present invention
[1]
Formula (1)
(式中、nは0から3の整数を示す。)で示されるポリイソシアナート化合物;
[2]
式(2)
(Wherein n represents an integer of 0 to 3);
[2]
Formula (2)
で示される[1] 記載のポリイソシアナート化合物;
[3]
式(3)
[1] The polyisocyanate compound according to [1];
[3]
Formula (3)
[式中、nは0から3の整数を示す。Rはアミノ基を示す。]をホスゲンと反応させることを特徴とする、式(1)のポリイソシアナート化合物の製造方法; [Wherein n represents an integer of 0 to 3. R represents an amino group. A process for producing a polyisocyanate compound of the formula (1), characterized in that
(式中、nは0から3の整数を示す。)
[4]
式(3)
(In the formula, n represents an integer of 0 to 3.)
[4]
Formula (3)
[式中、nは0から3の整数を示す。Rは−NHCO2R1(R1は炭素数1から4のアルキル基を示す)を示す。]を、塩基およびシリルハライドの存在下に分解反応させることを特徴とする式(1)のポリイソシアナート化合物の製造方法; [Wherein n represents an integer of 0 to 3. R represents —NHCO 2 R 1 (R 1 represents an alkyl group having 1 to 4 carbon atoms). In the presence of a base and a silyl halide, a process for producing a polyisocyanate compound of formula (1);
(式中、nは0から3の整数を示す。)
[5]
式(3)
(In the formula, n represents an integer of 0 to 3.)
[5]
Formula (3)
[式中、nは0から3の整数を示す。Rは−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示す。]
をクルチウス転位反応、ホフマン転位反応またはロッセン転位反応させることを特徴とする、式(1)のポリイソシアナート化合物の製造方法;
[Wherein n represents an integer of 0 to 3. R represents any one of —CO 2 R 1 and COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents any one of —N 3 , —NH 2 , and —NHOH). ]
A process for producing a polyisocyanate compound of the formula (1), characterized in that a Curtius rearrangement reaction, a Hoffman rearrangement reaction or a Rossen rearrangement reaction is carried out;
[6]
式(3)
[6]
Formula (3)
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示す。]で示される化合物;
[7]
式(4)
[Wherein n represents an integer of 0 to 3. R is an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is any one of —N 3 , —NH 2 , and —NHOH. .) ] The compound shown by
[7]
Formula (4)
で示される[6]に記載の化合物;
[8]
式(5)
The compound according to [6], which is represented by:
[8]
Formula (5)
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示し、R’は、−OR1(R1は前記と同義)を示す。]で示される化合物から製造される式(3)の化合物の製造方法; [Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) And R ′ represents —OR 1 (R 1 is as defined above). ] The manufacturing method of the compound of Formula (3) manufactured from the compound shown by;
[式中、n、Rは前記と同義。]
[9]
式(5)
[Wherein, n and R are as defined above. ]
[9]
Formula (5)
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示し、R’は、−OR1(R1は前記と同義)を示す。]で示される化合物;
[10]
式(6)
[Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) And R ′ represents —OR 1 (R 1 is as defined above). ] The compound shown by
[10]
Formula (6)
で示される[9]に記載の化合物;
[11]
式(5)
The compound according to [9], which is represented by:
[11]
Formula (5)
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示し、R’は、−OR1(R1は前記と同義)を示す。]で示される化合物から式(3)の化合物を経て製造される式(1)のポリイソシアナート化合物の製造方法; [Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) And R ′ represents —OR 1 (R 1 is as defined above). ] The manufacturing method of the polyisocyanate compound of Formula (1) manufactured through the compound of Formula (3) from the compound shown by;
[式中、n、Rは前記と同義。] [Wherein, n and R are as defined above. ]
[式中、nは前記と同義。]
[12]
[1]または[2]記載のポリイソシアナート化合物の少なくとも1つを構成モノマーとする重合性組成物;
[13]
[12]記載の重合性組成物を重合して得られる光学製品;
である。
[Wherein n is as defined above. ]
[12]
A polymerizable composition comprising at least one polyisocyanate compound according to [1] or [2] as a constituent monomer;
[13]
[12] An optical product obtained by polymerizing the polymerizable composition as described above;
It is.
本発明により、高屈折率樹脂の材料となる新規な1,3,5−トリチアン骨格を有するポリイソシアナート化合物が得られる。 According to the present invention, a novel polyisocyanate compound having a 1,3,5-trithiane skeleton, which is a material for a high refractive index resin, can be obtained.
以下に本発明を説明する。本発明は新規な1,3,5−トリチアン骨格を有するポリイソシアナート化合物およびその中間体と重合物および重合物からなる光学製品に関する。 The present invention will be described below. The present invention relates to a novel polyisocyanate compound having a 1,3,5-trithiane skeleton, an intermediate thereof, a polymer, and an optical product comprising the polymer.
本発明の新規な1,3,5−トリチアン骨格を有するポリイソシアナート化合物は、
式(1)
The polyisocyanate compound having a novel 1,3,5-trithiane skeleton of the present invention is
Formula (1)
(式中、nは0から3の整数を示す。)で示されるポリイソシアナート化合物、または
式(2)
(Wherein n represents an integer of 0 to 3), or the formula (2)
で示されるポリイソシアナート化合物である。
上記の1,3,5−トリチアン骨格を有するポリイソシアナート化合物は、式(3)
It is a polyisocyanate compound shown by.
The polyisocyanate compound having the 1,3,5-trithiane skeleton is represented by the formula (3)
[式中、nは前記と同義。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示す。]で示される中間体から得られる。 [Wherein n is as defined above. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) It is obtained from an intermediate represented by
例えば、中間体が、カルバミン酸エステル[式(3)でR=−NHCO2R1]の場合は、塩基存在下にシリルハライドと反応させることによりイソシアナートに誘導することができる[例えば、Angew.Chem.Int.Ed.,7(12),941(1968),Journal of the Organic Chemistry,63(23),8515(1998)に記載の方法を参考にすることができる]。 For example, when the intermediate is a carbamate ester [R = —NHCO 2 R 1 ] in the formula (3), it can be derivatized to an isocyanate by reacting with a silyl halide in the presence of a base [eg, Angew . Chem. Int. Ed. 7 (12), 941 (1968), Journal of the Organic Chemistry, 63 (23), 8515 (1998)].
中間体が、カルボン酸エステル類[一般式(3)でR=−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す)]は、クルティウス転位、ホフマン転位、ロッセン転位などの転位反応によりイソシアナートに誘導することができる[例えば、日本化学会編(丸善),第4版実験化学講座20巻,473−483に記載の方法を参考にすることができる]。 An intermediate is a carboxylic acid ester [in the general formula (3), R = —CO 2 R 1 , COR 2 (R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is —N 3 , —NH 2 , — Can be induced to isocyanate by rearrangement reactions such as Curtius rearrangement, Hoffman rearrangement, and Rossen rearrangement [for example, the Chemical Society of Japan (Maruzen), 4th edition, Experimental Chemistry Course, Volume 20 , 473-483, can be referred to].
中間体が、アミン類の場合はホスゲンとの反応や遷移金属触媒存在下一酸化炭素との反応などによりイソシアナートに誘導することができる[例えば、日本化学会編(丸善),第4版実験化学講座20巻,473−483に記載の方法を参考にすることができる]。 If the intermediate is an amine, it can be derived to an isocyanate by reaction with phosgene or carbon monoxide in the presence of a transition metal catalyst [for example, the Chemical Society of Japan (Maruzen), 4th edition experiment] The method described in Chemistry Lecture Volume 20, 473-483 can be referred to].
式(3)で示される中間体は、式(4) The intermediate represented by the formula (3) has the formula (4)
[式中、n、Rは前記と同義。R’は、−OR1(R1は前記と同義)を示す。]で示される化合物を酸触媒存在下に硫化水素と反応させることにより得られる。酸触媒としては、通常は硫酸等の鉱酸や3弗化ホウ素ジエチルエーテル錯体等のルイス酸が使用される。溶媒は特に限定はないが、通常クロロホルム等が好適に使用される。 [Wherein, n and R are as defined above. R ′ represents —OR 1 (R 1 is as defined above). Is obtained by reacting with hydrogen sulfide in the presence of an acid catalyst. As the acid catalyst, a mineral acid such as sulfuric acid or a Lewis acid such as boron trifluoride diethyl ether complex is usually used. The solvent is not particularly limited, but usually chloroform or the like is preferably used.
式(4)で示される化合物は、式(5) The compound represented by the formula (4) has the formula (5)
[式中、n、Rは前記と同義。R’は、−OR1(R1は前記と同義)を示す。]で表されるモノチオアセタール化合物を、塩基存在下、ジブロモメタン等と反応させることにより得られる。この反応において塩基は特に制限はないが、通常ナトリウムメトキサイド等が用いられる。溶媒は特に限定はないが、通常メタノール等が使用される。 [Wherein, n and R are as defined above. R ′ represents —OR 1 (R 1 is as defined above). Is obtained by reacting with a dibromomethane or the like in the presence of a base. In this reaction, the base is not particularly limited, but sodium methoxide or the like is usually used. The solvent is not particularly limited, but methanol or the like is usually used.
前記式(5)のモノチオアセタール化合物は、式(6) The monothioacetal compound of the formula (5) has the formula (6)
[式中、n、Rは前記と同義。R’は、−OR1(R1は前記と同義)を示す。]で示されるアセタール化合物を酸触媒存在下、チオ酢酸と反応させた後、さらに水酸化リチウム等のアルカリで加水分解することにより得ることができる。酸触媒は特に制限は無いが、四塩化チタンや塩化亜鉛等のルイス酸が使用される。溶媒は特に制限は無いが、クロロホルム等が用いられる。 [Wherein, n and R are as defined above. R ′ represents —OR 1 (R 1 is as defined above). The acetal compound can be obtained by reacting with thioacetic acid in the presence of an acid catalyst and further hydrolyzing with an alkali such as lithium hydroxide. The acid catalyst is not particularly limited, but Lewis acids such as titanium tetrachloride and zinc chloride are used. Although there is no restriction | limiting in particular in a solvent, Chloroform etc. are used.
本発明の1,3,5−トリチアン骨格を有するポリイソシアナートを構成モノマーとする重合性組成物は、
a)イソシアナート成分[式(1)の1,3,5−トリチアン骨格を有するポリイソシアナートの少なくとも一つを構成モノマーとする]、
b)チオール成分およびc)添加剤成分
からなるものである。
A polymerizable composition comprising a polyisocyanate having a 1,3,5-trithiane skeleton of the present invention as a constituent monomer,
a) isocyanate component [with at least one polyisocyanate having a 1,3,5-trithiane skeleton of formula (1) as a constituent monomer],
It consists of b) thiol component and c) additive component.
a)イソシアナート成分は、式(1)の1,3,5−トリチアン骨格を有するポリイソシアナートの少なくとも1つに加えて、光学材料の物性を適宜改良する目的で、式(1)のポリイソシアナート以外のポリイソシアナートを含有しても良い。その場合、式(1)のポリイソシアナートの使用量は全ポリイソシアナート中、5%モル以上であり、好ましくは25%モル以上、さらに好ましくは50%モル以上である。 a) In addition to at least one of the polyisocyanates having a 1,3,5-trithiane skeleton of the formula (1), the isocyanate component is used for the purpose of appropriately improving the physical properties of the optical material. Polyisocyanates other than isocyanates may be contained. In that case, the amount of the polyisocyanate of the formula (1) used is 5% mol or more, preferably 25% mol or more, more preferably 50% mol or more in all polyisocyanates.
式(1)の1,3,5−トリチアン骨格を有するポリイソシアナート以外のポリイソシアナートとしては、特に制限はないが、m−キシリレンジイソシアナート、ヘキサメチレンジイソシアナート、ビス(イソシアナトエチル)スルフィド、ビス(イソシアナトプロピル)スルフィド、 2,5−ジイソシアナトチオフェン、2,5−ビス(イソシアナトメチル)チオフェン、3,4−ビス(イソシアナトメチル)テトラヒドロチオフェン、2,5−ジイソシアナト−1,4−ジチアン、2,5−ビス(イソシアナトメチル)−1,4−ジチアン、4,5−ジイソシアナト−1,3−ジチオラン、4,5−ビス(イソシアナトメチル)−1,3−ジチオラン、4,5−ビス(イソシアナトメチル)−2−メチル−1,3−ジチオラン等をあげることができる。 The polyisocyanate other than the polyisocyanate having a 1,3,5-trithiane skeleton of the formula (1) is not particularly limited, but m-xylylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatoethyl) ) Sulfide, bis (isocyanatopropyl) sulfide, 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato -1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3 -Dithiolane, 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane, etc. It is possible.
b)チオール成分は、メタンジチオール、1,2-エタンジチオール、1,1-プロパンジチオール、1,2-プロパンジチオール、1,3-プロパンジチオール、2,2-プロパンジチオール、1,4-ブタンジチオール、2,3-ブタンジチオール、1,5-ペンタンジチオール、1,6-ヘキサンジチオール、1,2,3-プロパントリチオール、1,1-シクロヘキサンジチオール、1,2-シクロヘキサンジチオール、2,2-ジメチルプロパン-1,3-ジチオール、3,4-ジメトキシブタン-1,2-ジチオール、2-メチルシクロヘキサン-2,3-ジチオール、1,1-ビス(メルカプトメチル)シクロヘキサン、1,2-ジメルカプトプロピルメチルエーテル、2,3-ジメルカプトプロピルメチルエーテル、2,2-ビス(メルカプトメチル)-1,3-プロパンジチオール、ビス(2-メルカプトエチル)エーテル、テトラキス(メルカプトメチル)メタン、1,2-ビス(2−メルカプトエチルチオ)−3−プロパンチオール等の脂肪族チオール化合物及び、 b) The thiol component is methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2- Dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, 1,2-dimercapto Propyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3- B Panaji thiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, 1,2-bis (2-mercaptoethyl thio) -3 aliphatic thiol compound of propanethiol and the like and,
2,3-ジメルカプトコハク酸(2-メルカプトエチルエステル)、チオリンゴ酸ビス(2-メルカプトエチルエステル)、2,3-ジメルカプト-1-プロパノール(2-メルカプトアセテート)、2,3-ジメルカプト-1-プロパノール(3-メルカプトプロピオネート)、3-メルカプト-1,2-プロパンジオールジ(2-メルカプトアセテート)、3-メルカプト-1,2-プロパンジオールジ(3-メルカプトプロピオネート)、ジエチレングリコールビス(2-メルカプトアセテート)、ジエチレングリコールビス(3-メルカプトプロピオネート)、エチレングリコールビス(2-メルカプトアセテート)、エチレングリコールビス(3-メルカプトプロピオネート)、トリメチロールプロパントリス(2-メルカプトアセテート)、トリメチロールプロパントリス(3-メルカプトプロピオネート)、トリメチロールエタントリス(2-メルカプトアセテート)、トリメチロールエタントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(2-メルカプトアセテート)、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、グリセリントリス(2-メルカプトアセテート)、グリセリントリス(3-メルカプトプロピオネート)、1,4-シクロヘキサンジオールビス(2-メルカプトアセテート)、1,4-シクロヘキサンジオールビス(3-メルカプトプロピオネート)等のエステル結合を含む脂肪族チオール化合物、 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1 -Propanol (3-mercaptopropionate), 3-mercapto-1,2-propanediol di (2-mercaptoacetate), 3-mercapto-1,2-propanediol di (3-mercaptopropionate), diethylene glycol Bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate) ), Trimethylol propa Tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethanetris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3- Mercaptopropionate), glycerin tris (2-mercaptoacetate), glycerin tris (3-mercaptopropionate), 1,4-cyclohexanediol bis (2-mercaptoacetate), 1,4-cyclohexanediol bis (3- An aliphatic thiol compound containing an ester bond such as mercaptopropionate),
1,2-ジメルカプトベンゼン、1,3-ジメルカプトベンゼン、1,4-ジメルカプトベンゼン、1,2-ビス(メルカプトメチル)ベンゼン、1,3-ビス(メルカプトメチル)ベンゼン、1,4-ビス(メルカプトメチル)ベンゼン、1,2-ビス(メルカプトエチル)ベンゼン、1,3-ビス(メルカプトエチル)ベンゼン、1,4-ビス(メルカプトエチル)ベンゼン、1,2-ビス(メルカプトメチレンオキシ)ベンゼン、1,3-ビス(メルカプトメチレンオキシ)ベンゼン、1,4-ビス(メルカプトメチレンオキシ)ベンゼン、1,2-ビス(メルカプトエチレンオキシ)ベンゼン、1,3-ビス(メルカプトエチレンオキシ)ベンゼン、1,4-ビス(メルカプトエチレンオキシ)ベンゼン、1,2,3-トリメルカプトベンゼン、1,2,4-トリメルカプトベンゼン、1,3,5-トリメルカプトベンゼン、1,2,3-トリス(メルカプトメチル)ベンゼン、1,2,4-トリス(メルカプトメチル)ベンゼン、1,3,5-トリス(メルカプトメチル)ベンゼン、1,2,3-トリス(メルカプトエチル)ベンゼン、1,2,4-トリス(メルカプトエチル)ベンゼン、1,3,5-トリス(メルカプトエチル)ベンゼン、1,2,3-トリス(メルカプトメチレンオキシ)ベンゼン、1,2,4-トリス(メルカプトメチレンオキシ)ベンゼン、1,3,5-トリス(メルカプトメチレンオキシ)ベンゼン、1,2,3-トリス(メルカプトエチレンオキシ)ベンゼン、1,2,4-トリス(メルカプトエチレンオキシ)ベンゼン、1,3,5-トリス(メルカプトエチレンオキシ)ベンゼン、2,5-トルエンジチオール、3,4-トルエンジチオール、1,3-ジ(p-メトキシフェニル)プロパン-2,2-ジチオール、1,3-ジフェニルプロパン-2,2-ジチオール、フェニルメタン-1,1-ジチオール、2,4-ジ(p-メルカプトフェニル)ペンタン、1,4-ナフタレンジチオール、1,5-ナフタレンジチオール、2,6-ナフタレンジチオール、2,7-ナフタレンジチオール、2,4-ジメチルベンゼン-1,3-ジチオール、4,5-ジメチルベンゼン-1,3-ジチオール、9,10-アントラセンジメタンチオール、1,2,3,4-テトラメルカプトベンゼン、1,2,3,5-テトラメルカプトベンゼン、1,2,4,5-テトラメルカプトベンゼン、1,2,3,4-テトラキス(メルカプトメチル)ベンゼン、1,2,3,5-テトラキス(メルカプトメチル)ベンゼン、1,2,4,5-テトラキス(メルカプトメチル)ベンゼン、1,2,3,4-テトラキス(メルカプトエチル)ベンゼン、1,2,3,5-テトラキス(メルカプトエチル)ベンゼン、1,2,4,5-テトラキス(メルカプトエチル)ベンゼン、1,2,3,4-テトラキス(メルカプトメチレンオキシ)ベンゼン、1,2,3,5-テトラキス(メルカプトメチレンオキシ)ベンゼン、1,2,4,5-テトラキス(メルカプトメチレンオキシ)ベンゼン、1,2,3,4-テトラキス(メルカプトエチレンオキシ)ベンゼン、1,2,3,5-テトラキス(メルカプトエチレンオキシ)ベンゼン、1,2,4,5-テトラキス(メルカプトエチレンオキシ)ベンゼン、2,2´-ジメルカプトビフェニル、4,4´-ジメルカプトビフェニル、4,4´-ジメルカプトビベンジル、2,5-ジクロロベンゼン-1,3-ジチオール、1,3-ジ(p-クロロフェニル)プロパン-2,2-ジチオール、3,4,5-トリブロム-1,2-ジメルカプトベンゼン、2,3,4,6-テトラクロル-1,5-ビス(メルカプトメチル)ベンゼン等の芳香族チオール化合物及び、 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyleneoxy) Benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4 -Trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercapto) Methyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (Mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1 , 2,4-Tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1 , 1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4- Dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,2,3,4-tetramercaptobenzene, 1,2,3,5 -Tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-teto Kis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) Benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1 , 2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2 , 4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobiphenyl, 4, '-Dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4 Aromatic thiol compounds such as, 5-tribromo-1,2-dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene,
2-メチルアミノ-4,6-ジチオール-sym-トリアジン、2-エチルアミノ-4,6-ジチオール-sym-トリアジン、2-アミノ-4,6-ジチオール-sym-トリアジン、2-モルホリノ-4,6-ジチオール-sym-トリアジン、2-シクロヘキシルアミノ-4,6-ジチオール-sym-トリアジン、2-メトキシ-4,6-ジチオール-sym-トリアジン、2-フェノキシ-4,6-ジチオール-sym-トリアジン、2-チオベンゼンオキシ-4,6-ジチオール-sym-トリアジン、2-チオブチルオキシ-4,6-ジチオール-sym-トリアジン等の複素環チオール化合物及び、それらのハロゲン置換化合物、 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino-4 6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine Heterocyclic thiol compounds such as 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine, and halogen-substituted compounds thereof;
1,1,3,3−テトラキス(メルカプトメチルチオ)プロパン、1,1,2,2−テトラキス(メルカプトメチルチオ)エタン、4,6−ビス(メルカプトメチルチオ)−1,3−ジチアン、4,6−ビス(メルカプトメチルチオ)−1,3−ジチアシクロヘキサン、1,1,5,5−テトラキス(メルカプトメチルチオ)−3−チアペンタン、1,1,6,6−テトラキス(メルカプトメチルチオ)−3,4−ジチアヘキサン、2,2−ビス(メルカプトメチルチオ)エタンチオール、2−(4,5−ジメルカプト−2−チアペンチル)−1,3−ジチアシクロペンタン、2,2−ビス(メルカプトメチル)−1,3−ジチアシクロペンタン、2,5−ビス(4,4−ビス(メルカプトメチルチオ)−2−チアブチル)−1,4−ジチアン、2,2−ビス(メルカプトメチルチオ)−1,3−プロパンジチオール、3−メルカプトメチルチオ−1,7−ジメルカプト−2,6−ジチアヘプタン、3,6−ビス(メルカプトメチルチオ)−1,9−ジメルカプト−2,5,8−トリチアノナン、4,6−ビス(メルカプトメチルチオ)−1,9−ジメルカプト−2,5,8−トリチアノナン、3−メルカプトメチルチオ−1,6−ジメルカプト−2,5−ジチアヘキサン、2−(2,2−ビス(メルカプトメチルチオ)エチル)−1,3−ジチエタン、更にこれらのオリゴマー等のジチオアセタールもしくはジチオケタール骨格を有する化合物(ポリチオールに限らない。)等を挙げることができるが、これら例示化合物のみに限定されるものではない。 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 4,6- Bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1,1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4- Dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3 -Dithiacyclopentane, 2,5-bis (4,4-bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithia 2,2-bis (mercaptomethylthio) -1,3-propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto -2,5,8-trithianonane, 4,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, Examples thereof include 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, and compounds having a dithioacetal or dithioketal skeleton such as these oligomers (not limited to polythiol). It is not limited only to these exemplary compounds.
さらにこれらの塩素置換体、臭素置換体等のハロゲン置換体を使用しても良い。これらチオール化合物は単独でも、2種類以上を混合しても使用することができる。 Further, halogen-substituted products such as chlorine-substituted products and bromine-substituted products may be used. These thiol compounds can be used alone or in combination of two or more.
c)添加剤成分としては、重合反応促進のための重合触媒、耐光性改良のための紫外線吸収剤、酸化防止剤、着色防止剤、蛍光染料、光安定剤、内部離型剤等の添加剤を必要に応じて適宜加えても良い。
本発明で得られる重合組成物は、眼鏡レンズ、カメラレンズ等の光学材料用途のほか、ウレタン樹脂として塗料、接着剤としても好適である。
c) Additive components include polymerization catalysts for promoting polymerization reaction, ultraviolet absorbers for improving light resistance, antioxidants, anti-coloring agents, fluorescent dyes, light stabilizers, internal mold release agents, etc. May be added as necessary.
The polymerized composition obtained in the present invention is suitable for use as an optical material such as a spectacle lens and a camera lens, as a paint as a urethane resin, and as an adhesive.
(実施例1)
[2−メトキシ−2−(1−メトキシ−2−メトキシカルボニルアミノ−エチルスルファニルメチルスルファニル)−エチル]カルバミン酸メチルの製造
1−1. 2−アセチルチオ−2−メトキシエチルカルバミン酸メチル(2)の製造
(Example 1)
1. Preparation of [2-methoxy-2- (1-methoxy-2-methoxycarbonylamino-ethylsulfanylmethylsulfanyl) -ethyl] methyl carbamate 1-1. Production of methyl 2-acetylthio-2-methoxyethylcarbamate ( 2 )
1)カルバモイル化
アミノアセトアルデヒドジメチルアセタール(1;市販品:50g)のメタノール(350g)溶液へ、炭酸水素ナトリウム(100g)を装入後、冷却下(5℃)クロロギ酸メチル(90g)をゆっくり滴下装入した。同じ温度で4時間、室温でさらに24時間攪拌した。無機塩をろ過で除去した後、減圧濃縮した。濃縮物に水および酢酸エチルを加え抽出を行った。得られた有機層を水洗し、次に硫酸マグネシウムにて乾燥後、減圧濃縮して油状の2,2,−ジメトキシエチルカルバミン酸メチル(83g)を得た。これ以上の精製は行わず次工程にそのまま用いた。
1H−NMR(CDCl3):3.2−3.3(2H,m),3.40(6H,s),3.68(3H,s),4.37(1H,t,J=5.4Hz),4.90(1H,br.s).
2)チオアセチル化
2,2,−ジメトキシエチルカルバミン酸メチル(10.2g)のクロロホルム(50ml)溶液にチオ酢酸(15g)を装入した。これに、冷却下(−20℃)4塩化チタン(1.8g)を滴下装入した。室温に戻した後さらに24時間攪拌した。反応液に氷片を加えてしばらく攪拌した後、クロロホルムと水を加え抽出を行った。有機層を水洗し、次に硫酸マグネシウムにて乾燥後、減圧濃縮して油状物を得た。これをシリカゲルカラム(酢酸エチル−ヘキサンステップワイズで溶出)で精製を行い、2−アセチルチオ−2−メトキシエチルカルバミン酸メチル(13.7g)を得た(収率52%)。
1H−NMR(CDCl3):2.39(3H,s),3.37(3H,s),3.5−3.6(2H,m),3.69(3H,s),5.08(1H,br.s),5.3(1H,m).
1−2. 2−メルカプト−2−メトキシエチルカルバミン酸メチル(3)の製造
1) Carbamoylation Sodium hydrogen carbonate (100 g) was charged into a methanol (350 g) solution of aminoacetaldehyde dimethyl acetal ( 1 ; commercial product: 50 g), and then methyl chloroformate (90 g) was slowly added dropwise under cooling (5 ° C.). I was charged. The mixture was stirred at the same temperature for 4 hours and at room temperature for another 24 hours. The inorganic salt was removed by filtration and then concentrated under reduced pressure. Water and ethyl acetate were added to the concentrate for extraction. The obtained organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain oily methyl 2,2, -dimethoxyethylcarbamate (83 g). The product was used in the next step without further purification.
1 H-NMR (CDCl 3 ): 3.2-3.3 (2H, m), 3.40 (6H, s), 3.68 (3H, s), 4.37 (1H, t, J = 5.4 Hz), 4.90 (1H, br.s).
2) Thioacetylation A solution of methyl 2,2, -dimethoxyethylcarbamate (10.2 g) in chloroform (50 ml) was charged with thioacetic acid (15 g). To this was added dropwise titanium tetrachloride (1.8 g) under cooling (−20 ° C.). After returning to room temperature, the mixture was further stirred for 24 hours. Ice pieces were added to the reaction solution and stirred for a while, followed by extraction with chloroform and water. The organic layer was washed with water, then dried over magnesium sulfate and concentrated under reduced pressure to give an oil. This was purified with a silica gel column (eluted with ethyl acetate-hexane stepwise) to obtain methyl 2-acetylthio-2-methoxyethylcarbamate (13.7 g) (yield 52%).
1 H-NMR (CDCl 3 ): 2.39 (3H, s), 3.37 (3H, s), 3.5-3.6 (2H, m), 3.69 (3H, s), 5 .08 (1H, br.s), 5.3 (1H, m).
1-2. Production of methyl 2-mercapto-2-methoxyethylcarbamate ( 3 )
2−アセチルチオ−2−メトキシエチルカルバミン酸メチル(62g)のメタノール(500ml)溶液に、冷却下(−20℃)水酸化リチウム1水和物(13.7g)を徐々に装入した。同温度で2時間反応後、減圧濃縮して油状物を得た。これに水、酢酸エチルを加えた後、氷冷下塩酸で中和を行った。有機層を水洗、乾燥(硫酸マグネシウム)後、減圧濃縮して油状物(57g)を得た。これ以上の精製は行わず、次の工程に用いた。
1H−NMR(CDCl3):1.74(1H,d,J=8.8Hz),3.4−3.5(1H,m),3.43(3H,s),3.6−3.7(1H,m),3.69(3H,s),4.52(1H,m),5.17(1H,br.s).
1−3. [2−メトキシ−2−(1−メトキシ−2−メトキシカルボニルアミノ−エチルスルファニルメチルスルファニル)−エチル]カルバミン酸メチル(4)
A solution of methyl 2-acetylthio-2-methoxyethylcarbamate (62 g) in methanol (500 ml) was gradually charged with lithium hydroxide monohydrate (13.7 g) under cooling (−20 ° C.). After reacting at the same temperature for 2 hours, it was concentrated under reduced pressure to obtain an oily substance. Water and ethyl acetate were added thereto, followed by neutralization with hydrochloric acid under ice cooling. The organic layer was washed with water, dried (magnesium sulfate), and concentrated under reduced pressure to give an oil (57 g). It was used in the next step without further purification.
1 H-NMR (CDCl 3 ): 1.74 (1H, d, J = 8.8 Hz), 3.4-3.5 (1H, m), 3.43 (3H, s), 3.6- 3.7 (1H, m), 3.69 (3H, s), 4.52 (1H, m), 5.17 (1H, br.s).
1-3. [2-Methoxy-2- (1-methoxy-2-methoxycarbonylamino-ethylsulfanylmethylsulfanyl) -ethyl] methyl carbamate ( 4 )
2−メルカプト−2−メトキシエチルカルバミン酸メチル(49g)、ジブロモメタン(72g)、メタノール(400ml)の混合物へ、冷却下(3℃)28%ナトリウムメトキシド/メタノール溶液を滴下装入した。徐々に室温まで昇温した後、24時間攪拌した。反応液を濃縮後、水、酢酸エチルを加え抽出を行った。有機層を水洗、乾燥(硫酸マグネシウム)後、減圧濃縮して油状物を得た。これをシリカゲルカラム(ヘキサン−酢酸エチルステップワイズで溶出)で精製を行い、油状の目的物(25g、収率49%)を得た。
1H−NMR(CDCl3):δ3.44(6H,s),3.5−3.6(4H,m),3.69(6H,s),3.72(2H,s),4.55(2H,m),5.25(2H,br.s).
FAB−MS(positive,matrix:m−nitrobenzylalcohol):m/z343(MH+).
(実施例2)
2,4−ビスメトキシカルボニルメチル−1,3,5−トリチアンの製造
To a mixture of methyl 2-mercapto-2-methoxyethylcarbamate (49 g), dibromomethane (72 g), and methanol (400 ml), a 28% sodium methoxide / methanol solution was charged dropwise with cooling (3 ° C.). The mixture was gradually warmed to room temperature and stirred for 24 hours. The reaction solution was concentrated and extracted with water and ethyl acetate. The organic layer was washed with water, dried (magnesium sulfate) and concentrated under reduced pressure to give an oil. This was purified with a silica gel column (eluted with hexane-ethyl acetate stepwise) to obtain an oily target product (25 g, yield 49%).
1 H-NMR (CDCl 3 ): δ 3.44 (6H, s), 3.5-3.6 (4H, m), 3.69 (6H, s), 3.72 (2H, s), 4 .55 (2H, m), 5.25 (2H, br.s).
FAB-MS (positive, matrix: m-nitrobenzyl alcohol): m / z 343 (MH <+> ).
(Example 2)
Production of 2,4-bismethoxycarbonylmethyl-1,3,5-trithiane
化合物4(10g)のクロロホルム溶液(200ml)へ冷却下(−10℃)3フッ化ホウ素エチルエーテル錯体(10g)のクロロホルム溶液を滴下装入した。これに硫化水素ガス吹き込みを開始し2時間かけて室温まで昇温した。硫化水素の吹き込み終了後さらに室温で2時間攪拌した。氷片を装入後に分液を行った。有機層をさらに水洗後、硫酸マグネシウムで乾燥した。これをろ過、濃縮後にメタノールを装入して晶析を行った。析出した固体をろ集して目的物2,4−ビスメトキシカルボニルメチル−1,3,5−トリチアン(2.2g,収率24%)を得た。
1H−NMR(DMSO−d6):δ3.2−3.3(4H,m),3.56(6H,s),4.19(1H,d,J=14Hz),4.43(1H,d,J=14Hz),4.55(2H,t,J=6.8Hz),7.51(2H,t).
FAB−MS(positive,matrix:m−nitrobenzylalcohol):m/z313(MH+).
(実施例3)
2,4−ビスイソシアナトメチル−1,3,5−トリチアンの製造
A chloroform solution of boron trifluoride ethyl ether complex (10 g) was added dropwise to a chloroform solution (200 ml) of compound 4 (10 g) under cooling (−10 ° C.). Hydrogen sulfide gas blowing was started and the temperature was raised to room temperature over 2 hours. After completion of the hydrogen sulfide blowing, the mixture was further stirred at room temperature for 2 hours. Liquid separation was carried out after charging ice pieces. The organic layer was further washed with water and dried over magnesium sulfate. After filtration and concentration, crystallization was performed by charging methanol. The precipitated solid was collected by filtration to obtain the desired product 2,4-bismethoxycarbonylmethyl-1,3,5-trithiane (2.2 g, yield 24%).
1 H-NMR (DMSO-d 6 ): δ 3.2-3.3 (4H, m), 3.56 (6H, s), 4.19 (1H, d, J = 14 Hz), 4.43 ( 1H, d, J = 14 Hz), 4.55 (2H, t, J = 6.8 Hz), 7.51 (2H, t).
FAB-MS (positive, matrix: m-nitrobenzylcohol): m / z 313 (MH <+> ).
(Example 3)
Production of 2,4-bisisocyanatomethyl-1,3,5-trithiane
2,4−ビスメトキシカルボニルメチル−1,3,5−トリチアン(1g)にトルエン(40ml)、トリエチルアミン(1.3g)、クロロトリメチルシラン(1.9g)を順次装入し、窒素雰囲気下70℃にて10時間反応した。冷却後に副生したトリエチルアミン塩酸塩をろ過で除去してから、ろ液を減圧濃縮して油状物を得た。これを−20℃に冷却して析出した固体をヘキサンで洗浄して、粉末状固体の目的物2,4−ビスイソシアナトメチル−1,3,5−トリチアン(0.76g,収率96%)を得た。
1H−NMR(CDCl3):δ3.72(4H,d,J=6.4Hz),4.21(1H,d,J=14Hz),4.31(1H,15Hz),4.45(2H,t,J=6.2Hz).
EI−MS(positive):m/z248(M+).
IR(KBr):2283cm−1.
(実施例4)
2,4−ビスイソシアナトメチル−1,3,5−トリチアンの製造
触媒としてジブチル錫ジクロライドを200ppm(wt/wt)および内部離型剤として酸性リン酸エステル(商品名ZelecUN)を1000ppm(wt/wt)溶解したm−キシリレンジイソシアナート(1g)、2,4−ビスイソシアナトメチル−1,3,5−トリチアン(0.64g)、1,1,3,3−テトラキス(メルカプトメチルチオ)プロパンおよび4,6−ビス(メルカプトメチルチオ)−1,3−ジチアンおよび2−(2,2−ビス(メルカプトメチルチオ)エチル)−1,3−ジチエタンの混合物(1.64g)を混合して均一液とした。孔径3μmのメンブランフィルターでろ過して十分脱泡を行った後、オーブン中で50℃〜80℃まで徐々に昇温して60時間重合した。重合終了後離型して樹脂を得た。得られた樹脂の屈折率(ne)は1.695であった。
Toluene (40 ml), triethylamine (1.3 g), and chlorotrimethylsilane (1.9 g) were sequentially added to 2,4-bismethoxycarbonylmethyl-1,3,5-trithiane (1 g), and the atmosphere was 70 under a nitrogen atmosphere. The reaction was carried out at ° C for 10 hours. Triethylamine hydrochloride formed as a by-product after cooling was removed by filtration, and then the filtrate was concentrated under reduced pressure to obtain an oily substance. This was cooled to −20 ° C., and the precipitated solid was washed with hexane to give the desired product 2,4-bisisocyanatomethyl-1,3,5-trithiane (0.76 g, yield 96%) as a powdery solid. )
1 H-NMR (CDCl 3 ): δ 3.72 (4H, d, J = 6.4 Hz), 4.21 (1H, d, J = 14 Hz), 4.31 (1H, 15 Hz), 4.45 ( 2H, t, J = 6.2 Hz).
EI-MS (positive): m / z 248 (M <+> ).
IR (KBr): 2283 cm −1 .
Example 4
Production of 2,4-bisisocyanatomethyl-1,3,5-trithiane 200 ppm (wt / wt) of dibutyltin dichloride as a catalyst and 1000 ppm (wt / wt) of an acidic phosphate ester (trade name ZelecUN) as an internal mold release agent wt) dissolved m-xylylene diisocyanate (1 g), 2,4-bisisocyanatomethyl-1,3,5-trithiane (0.64 g), 1,1,3,3-tetrakis (mercaptomethylthio) propane And a mixture (1.64 g) of 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane were mixed to obtain a uniform solution It was. After sufficiently defoaming by filtration through a membrane filter having a pore size of 3 μm, the temperature was gradually raised from 50 ° C. to 80 ° C. in an oven and polymerized for 60 hours. After the polymerization was completed, the mold was released to obtain a resin. The obtained resin had a refractive index (ne) of 1.695.
Claims (13)
(式中、nは0から3の整数を示す。)で示されるポリイソシアナート化合物。 Formula (1)
(Wherein n represents an integer of 0 to 3).
で示される請求項1記載のポリイソシアナート化合物。 Formula (2)
The polyisocyanate compound of Claim 1 shown by these.
[式中、nは0から3の整数を示す。Rはアミノ基を示す。]をホスゲンと反応させることを特徴とする、式(1)のポリイソシアナート化合物の製造方法。
(式中、nは0から3の整数を示す。) Formula (3)
[Wherein n represents an integer of 0 to 3. R represents an amino group. ] With a phosgene, The manufacturing method of the polyisocyanate compound of Formula (1) characterized by the above-mentioned.
(In the formula, n represents an integer of 0 to 3.)
[式中、nは0から3の整数を示す。Rは−NHCO2R1(R1は炭素数1から4のアルキル基を示す)を示す。]を、塩基およびシリルハライドの存在下に分解反応させることを特徴とする、式(1)のポリイソシアナート化合物の製造方法。
(式中、nは0から3の整数を示す。) Formula (3)
[Wherein n represents an integer of 0 to 3. R represents —NHCO 2 R 1 (R 1 represents an alkyl group having 1 to 4 carbon atoms). ] In the presence of a base and a silyl halide, a process for producing a polyisocyanate compound of the formula (1),
(In the formula, n represents an integer of 0 to 3.)
[式中、nは0から3の整数を示す。Rは−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示す。]
をクルチウス転位反応、ホフマン転位反応またはロッセン転位反応させることを特徴とする、式(1)のポリイソシアナート化合物の製造方法。
[Wherein n represents an integer of 0 to 3. R represents any one of —CO 2 R 1 and COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents any one of —N 3 , —NH 2 , and —NHOH). ]
A process for producing a polyisocyanate compound of the formula (1), characterized by subjecting to a Curtius rearrangement reaction, a Hoffman rearrangement reaction or a Rossen rearrangement reaction.
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示す。]で示される化合物。 Formula (3)
[Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) ] The compound shown.
で示される請求項6に記載の化合物。 Formula (4)
The compound of Claim 6 shown by these.
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示し、R’は、−OR1(R1は前記と同義)を示す。]で示される化合物から製造される式(3)の化合物の製造方法。
[式中、n、Rは前記と同義。] Formula (5)
[Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) And R ′ represents —OR 1 (R 1 is as defined above). ] The manufacturing method of the compound of Formula (3) manufactured from the compound shown by this.
[Wherein, n and R are as defined above. ]
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示し、R’は、−OR1(R1は前記と同義)を示す。]で示される化合物。 Formula (5)
[Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) And R ′ represents —OR 1 (R 1 is as defined above). ] The compound shown.
で示される請求項9に記載の化合物。 Formula (6)
The compound of Claim 9 shown by these.
[式中、nは0から3の整数を示す。Rはアミノ基、−NHCO2R1、−CO2R1、COR2(R1は炭素数1から4のアルキル基、R2は−N3、−NH2、−NHOHのいずれかを示す。)のいずれかを示し、R’は、−OR1(R1は前記と同義)を示す。]で示される化合物から、式(3)の化合物を経て製造される式(1)のポリイソシアナート化合物の製造方法。
[式中、n、Rは前記と同義。]
[式中、nは前記と同義。] Formula (5)
[Wherein n represents an integer of 0 to 3. R represents an amino group, —NHCO 2 R 1 , —CO 2 R 1 , COR 2 (R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents any of —N 3 , —NH 2 , and —NHOH. .) And R ′ represents —OR 1 (R 1 is as defined above). ] The manufacturing method of the polyisocyanate compound of Formula (1) manufactured through the compound of Formula (3) from the compound shown by these.
[Wherein, n and R are as defined above. ]
[Wherein n is as defined above. ]
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JP5602741B2 (en) * | 2009-08-05 | 2014-10-08 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and method for producing optical material |
US10179830B2 (en) | 2014-06-13 | 2019-01-15 | Covestro Deutschland Ag | Thioallophanate polyisocyanates containing silane groups |
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JPS55102509A (en) * | 1979-01-29 | 1980-08-05 | Oreal | Cosmetic composition for hair and skin |
JPH05105677A (en) * | 1991-10-14 | 1993-04-27 | Hoya Corp | Polyisocyanate compound, optical material and optical product obtained by using the same |
JPH08208801A (en) * | 1994-11-17 | 1996-08-13 | Mitsui Toatsu Chem Inc | Composition for optical material and its use |
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JPS55102509A (en) * | 1979-01-29 | 1980-08-05 | Oreal | Cosmetic composition for hair and skin |
JPH05105677A (en) * | 1991-10-14 | 1993-04-27 | Hoya Corp | Polyisocyanate compound, optical material and optical product obtained by using the same |
JPH08208801A (en) * | 1994-11-17 | 1996-08-13 | Mitsui Toatsu Chem Inc | Composition for optical material and its use |
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JP5602741B2 (en) * | 2009-08-05 | 2014-10-08 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and method for producing optical material |
US9000119B2 (en) | 2009-08-05 | 2015-04-07 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, optical material, and method for producing optical material |
US10179830B2 (en) | 2014-06-13 | 2019-01-15 | Covestro Deutschland Ag | Thioallophanate polyisocyanates containing silane groups |
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