WO1993025386A1 - Thermally resistant glass article - Google Patents
Thermally resistant glass article Download PDFInfo
- Publication number
- WO1993025386A1 WO1993025386A1 PCT/US1993/001031 US9301031W WO9325386A1 WO 1993025386 A1 WO1993025386 A1 WO 1993025386A1 US 9301031 W US9301031 W US 9301031W WO 9325386 A1 WO9325386 A1 WO 9325386A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- article
- group
- compound
- coating composition
- maleimide
- Prior art date
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- 239000011521 glass Substances 0.000 title claims description 13
- 239000008199 coating composition Substances 0.000 claims abstract description 73
- -1 maleimide compound Chemical class 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 13
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002708 enhancing effect Effects 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 62
- 125000000524 functional group Chemical group 0.000 claims description 25
- 239000013307 optical fiber Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 16
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- 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 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- CNODSORTHKVDEM-UHFFFAOYSA-N 4-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=C(N)C=C1 CNODSORTHKVDEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006845 Michael addition reaction Methods 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- QRWVOJLTHSRPOA-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)urea Chemical compound C=CCNC(=O)NCC=C QRWVOJLTHSRPOA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 4
- ZRKLEAHGBNDKHM-UHFFFAOYSA-N N,n'-diallyl-2,3-dihydroxysuccinamide Chemical compound C=CCNC(=O)C(O)C(O)C(=O)NCC=C ZRKLEAHGBNDKHM-UHFFFAOYSA-N 0.000 claims description 4
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 4
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002241 glass-ceramic Substances 0.000 claims description 4
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 claims description 3
- OOXMQACSWCZQLX-UHFFFAOYSA-N 3,9-bis(ethenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OC(C=C)OCC21COC(C=C)OC2 OOXMQACSWCZQLX-UHFFFAOYSA-N 0.000 claims description 3
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- DBMSQTNESXMLCH-UHFFFAOYSA-N 1-[1-[2-(2,5-dioxopyrrol-1-yl)propoxy]propan-2-yl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C)COCC(C)N1C(=O)C=CC1=O DBMSQTNESXMLCH-UHFFFAOYSA-N 0.000 claims description 2
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 claims description 2
- FJKKJQRXSPFNPM-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(N2C(C=CC2=O)=O)C=C1N1C(=O)C=CC1=O FJKKJQRXSPFNPM-UHFFFAOYSA-N 0.000 claims description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 2
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 claims description 2
- QEEZSWGDNCHFKC-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-ylmethyl)-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CC1=NCCO1 QEEZSWGDNCHFKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 150000004678 hydrides Chemical group 0.000 claims 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 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 claims 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 claims 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims 2
- 229930003836 cresol Natural products 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- BJZCDNCLJBJENV-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]-3-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C(C=2C=CC=CC=2)=CC1=O BJZCDNCLJBJENV-UHFFFAOYSA-N 0.000 claims 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 claims 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 34
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 26
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 239000001294 propane Substances 0.000 description 17
- 230000035882 stress Effects 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 150000001282 organosilanes Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- JEAPEYGGHJNSII-UHFFFAOYSA-N 1-(4-morpholin-4-ylphenyl)butan-2-one Chemical compound C1=CC(CC(=O)CC)=CC=C1N1CCOCC1 JEAPEYGGHJNSII-UHFFFAOYSA-N 0.000 description 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 description 1
- IKFPAKYBSYICFK-UHFFFAOYSA-N 1-[4-(4-propylphenoxy)phenyl]pyrrole-2,5-dione Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 IKFPAKYBSYICFK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical group CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- PJUQAFXJSAHTEG-UHFFFAOYSA-N 4-amino-2-(oxiran-2-ylmethyl)phenol Chemical compound NC1=CC=C(O)C(CC2OC2)=C1 PJUQAFXJSAHTEG-UHFFFAOYSA-N 0.000 description 1
- WOYZXEVUWXQVNV-UHFFFAOYSA-N 4-phenoxyaniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1 WOYZXEVUWXQVNV-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- OSWZZATXSQBLAN-UHFFFAOYSA-N 6-(7-oxabicyclo[4.1.0]heptan-4-ylmethyl)-7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1CC2OC2CC1CC12OC1CCC(C(=O)O)C2 OSWZZATXSQBLAN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical class C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 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 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MJVGBKJNTFCUJM-UHFFFAOYSA-N mexenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(C)C=C1 MJVGBKJNTFCUJM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000006235 propyl amino ethyl group Chemical group [H]N(C([H])([H])C([H])([H])*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4988—Organosilicium-organic copolymers, e.g. olefins with terminal silane groups
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
Definitions
- the present invention relates to strength
- Optical fibers include a small diameter fiber core having an index of refraction such that incident light may be internally reflected within the fiber core and thereby transmitted along the length of the fiber core.
- optical fiber cores are made from a brittle material, e.g. quartz or aluminosilicate glass. In order to enhance the strength of the
- a coating layer is typically applied onto the surface of the fiber core using, e.g. nylon, polyethylene,
- polyurethane, epoxy, silicone or acrylate coating compositions are polyurethane, epoxy, silicone or acrylate coating compositions.
- the performance of conventional optical fiber coating compositions is inadequate at temperatures greater than about 300 F and therefore limits the temperature range within which such optical fibers may be used.
- the thermally resistant optical fiber comprises a silaceous substrate and a coating layer on the substrate.
- the coating layer comprises the cured reaction product of a reactive coating composition.
- the reactive coating composition comprises a maleimide compound having at least one and preferably two maleimide functional groups per molecule.
- the thermally resistant article exhibits improved strength at elevated temperatures, is suitable for continuous use at temperatures up to about 400°C and is tolerant of brief excursions up to about 500°C.
- the silaceous substrate is selected from the group consisting of glasses, glass ceramics, silaceous ceramic materials and combinations thereof.
- the coating composition comprises a mixture of a maleimide compound having at least two maleimide functional groups per molecule and a silane coupling agent.
- the coating composition comprises a mixture of a maleimide compound having at least two maleimide functional groups per molecule and a comonomer.
- the thermally resistant article comprises an optical fiber.
- a method for enhancing the strength of a silaceous substrate includes applying a layer of a coating composition to the silaceous substrate wherein the coating composition comprises a maleimide compound having at least two maleimide functional groups per molecule and cross linking the coating composition to form a strength enhancing coating layer on the core.
- the FIGURE shows a plot of the weight (expressed as a percentage of original weight) of a sample of a thermally resistant optical fiber of the present invention versus temperature.
- the thermally resistant article of the present invention includes a silaceous substrate and a strength enhancing coating layer on the substrate.
- the silaceous substrate of the article of the present invention may comprise any silica-containing material, e.g. any glass, glass-ceramic, silaceous ceramic or combination thereof.
- suitable silaceous substrate materials include
- borosilicate glass silica, lithium aluminosilicate, KF glasses, and SSe glasses.
- the coating composition and process set forth herein may be used to increase the tensile and/or flexural strength of any silaceous substrate to provide strength enhanced elavated
- the coating compositions set forth herein may be used as an adhesive in glass/glass or glass/metal laminates, as a molding compound or as an encapsulant.
- the coating layer is the cured reaction product of a reactive coating composition.
- the reactive coating composition includes a maleimide compound.
- the maleimide compound of the coating composition of the present invention may be any compound which includes at least two reactive maleimide functional groups per molecule.
- the coating composition may include a mixture of maleimide compounds.
- the maleimide compound may be any maleimide compound according to the structural formula:
- R 1 and R 2 independently are hydrogen or lower
- R 3 is an organic linking group that lacks any functional groups that would interfere with preparation of the maleimide groups or with the reactivity of the maleimide groups formed;
- n 1 ;
- n 1 if n ⁇ 1.
- R 1 and R 2 are each hydrogen or
- R 1 and R 2 are each
- R 3 may be, e.g. an alkyl, cycloalkyl, aryl or aralkyl group and may be bonded to the maleimide groups through an oxygen atom.
- the oligomeric polyfunctional maleimide is of
- n is greater than 1 but less than about 10.
- An exemplary oligomeric polyfunctional maleimide is known as Thermax MP-2000X, is commercially available from Kennedy and Klim, Inc. of Little Silver, New Jersey and has the structural formula:
- Ml is a maleimide functional group
- R 4 is either H or CH 3 .
- Suitable bismaleimides may be prepared, e.g. by reaction of maleic anhydride with a suitable diamine.
- Suitable diamines include aromatic amino acids
- diamines e.g. 4,4'- , 2,4'-, 3,3'- and 2,2'- diaminophenylmethane, aliphatic diamines, e.g. hexa- methylenediamine, dodecamethylenediamine,
- cycloaliphatic diamines e.g. 1,4
- eyelohexylmethanediamine 3,3'-, 4,4'- 2,4' and 2,2' dicyclohexylmethanediamines and aralkyldiamines, e.g. xylylenediamine.
- suitable diamines for use in preparing bismaleimides include 4,4' diaminophenyl oxide, 1,3-bis [3-aminophenoxy] benzene, 2,2'-,
- Suitable bismaleimide compounds include N,N' ethylenedimaleimide, N,N' -hexamethylenedimaleimide, N,N'
- diphenylmethane) bismaleimide N,N' - 4 methyl - 1,3 -phenylene) bismaleimide, 6 - maleimido - 1 - (4' -maleimidophenyl) - 1,3,3 - trimethyl-indone, N,N' - o -phenylene - bismaleimide and N,N' p - phenylene
- the coating composition of the present invention may include from about 40 weight percent to about 99.5 weight percent of the maleimide compound. Preferably, the coating composition includes from about 60 weight percent to about 95 weight percent of the maleimide compound.
- the maleimide compound may be the sole
- the reactive coating composition may include a comonomer.
- comonomers include any monomeric species which may be copolymerized with the maleimide compound, e.g. epoxy resins, monomers having reactive acetylenically
- the comonomer is a multifunctional comonomer to provide a highly crosslinked cured
- a suitable epoxy resin comonomer is any monomeric or oligomeric compound which includes at least one epoxy, i.e. oxirane, functional group per molecule.
- Specific examples of epoxy compounds suitable as comonomers in the coating of the present invention include the diglycidyl ether of bisphenol A (such as EPON resins from Shell); glycidylethers of phenol or cresol-formaldehyde resins (e.g., epoxy novolac
- oligomers such as DOW DEN resins); cycloaliphatic monomers such as 1, 4-vinylcyclohexene dioxide,
- aliphatic glycidyl ethers such as trimethylolpropane triglycidylether and neopentyl glycol diglycidyl ether.
- Suitable comonomers having acetylenically or ethylenically unsaturated functional groups may be any monomeric compound having at least one acetylenically or ethylenically unsaturated functional group per molecule.
- Suitable unsaturated comonomers include acrylic acids as well as amides and esters derived therefrom, e.g. acrylic acid, methacrylic acid, methylmethacrylate, acrylamide,
- 1,3-Butylene glycol dimethacrylate also included are unsaturated materials such as, styrene,
- n-vinylpyrrolidone and maleate esters Unsaturated comonomers having multiple unsaturated sites are preferred.
- Diallyl and divinyl compounds have been found to be particularly suitable ethylenically unsaturated comonomers. Examples of suitable diallyl and divinyl compounds include diallyl phthalate,
- Suitable oxazoline comonomers include 2 - methyl oxazoline and bis (2 - oxazolinyl) methane.
- undergoing Michael addition reaction include primary amino compounds and thiol compounds.
- Specific and preferred examples include 3,3' diaminodiphenylsulfone and dicarboxylic acid dihydrazides, 1,4 - bis
- the coating composition of the present invention may include from about 0 weight percent to about 60 weight percent of the comonomer. Preferably, the coating composition includes from about 5 weight percent to about 30 weight percent of the comonomer.
- the reactive coating composition may include a silane coupling agent.
- Silane coupling agents suitable for use in the coating composition of the present invention include any organosilane monomer having one or more groups capable of reacting with the silaceous substrate and a nonhydrolyzable organic functional group capable of undergoing reaction to form a chemical bond with the maleimide compound described above.
- Suitable organosilane coupling agents are those of the general formula:
- R 4 is a nonhydrolyzable organic functional group which is capable of reacting with a
- maleimide functional group e.g.
- R 5 is a nonhydrolyzable nonfunctional
- organic group e.g. alkyl
- X is a hydroxyl group or hydrolyzable group, e.g. alkoxy, acetoxy, amino or halo;
- n 0, 1 or 2.
- the hydroxyl or hydrolyzable group X is capable of undergoing reaction with, or of undergoing hydrolysis and subsequent reaction with, silanol groups on the silaceous substrate to chemically bond the organosilane monomer to the surface of the substrate.
- nonhydrolyzable organic functional group is capable of undergoing reaction with the maleimide or with the comonomer of the coating composition to chemically bond the organosilane monomer within the cured coating layer.
- maleimide compound or a comonomer of the coating composition provide a chemical bonding between the cured coating layer and the silaceous substrate.
- n 0 or 1
- the organic functional group R is a group capable of undergoing free radical or cationic polymerization and the hydrolyzable group X is alkoxy.
- organosilane coupling agents include
- aminophenyltrimethoxysilane are particularly preferred as the organosilane. Mixtures of two or more
- organosilane coupling agents are also suitable as the organosilane coupling agent.
- the coating composition of the present invention may include from about 0.5 weight percent to about 20 weight percent of the silane coupling agent.
- the coating composition includes from about 5 weight percent to about 15 weight percent silane coupling agent.
- initiator compound may be cured by heating to a
- the coating composition may further comprise a polymerization initiator.
- the reactive maleimide coating composition may be cured by several different routes, i.e. the coating composition may be cured by photoinitiated free radial reactions, by thermally initiated free radical reactions, by cationic reactions, by Zwitterionic reactions, by cycloaddition reactions, by Michael addition reactions, by base catalyzed reactions and by combinations thereof.
- composition of the present invention are:
- photoinitiators which dissociate or decompose upon exposure to actinic radiation to yield a free radical.
- Conventional photosensitizing compounds may be used in combination with the photoinitiator.
- Photoinitiators which dissociate upon exposure to radiation having a wavelength in the range of 40 nm to 400 nm are examples of photoinitiators which dissociate upon exposure to radiation having a wavelength in the range of 40 nm to 400 nm.
- Suitable photoinitiator compounds include, e.g. benzil, benzophenone,
- camphorquinone benzoin n-butyl ether, thioxanthone, 2-hydroxy-methyl-1-phenyl-propan-1-one,
- photoinitiators include 2-hydroxy-methyl-1-phenyl-propan-1-one and 1-hydroxycyclohexylphenylketone.
- the coating composition of the present invention may be heat cured by including a thermal initiator, e.g. a compound which decomposes upon heating to yield free radical, in the coating composition.
- a thermal initiator e.g. a compound which decomposes upon heating to yield free radical
- the thermal initiator may be substituted for the photoinitiator to provide heat curable composition or may be included in addition to the photoinitiator to provide a composition that may be cured by exposure to heat and/or radiation.
- Suitable thermal initiators include, e.g.
- 1, 1'-azobis cyanocyclohexane
- 2, 2' azobis isobutylnitrile
- the coating composition of the present invention may be cured by a cationic reaction either thermally or photolytically, using a suitable acid initiator, e.g. onium salts, diazonium salts or
- the coating composition of the present invention may be cured by thermal reactions
- a compound having acid-base properties e.g. an imidazole derivative
- the coating composition as a polymerization initiator.
- the coating composition of the present invention may be cured by base catalyzed reactions by including a basic catalyst, e.g. a metal alkoxide, in the composition as a polymerization initiator.
- a basic catalyst e.g. a metal alkoxide
- the coating composition of the present invention may be cured by cycloaddition reaction if a triplet sensitizer or Lewis acid is included in the composition as a polymerization initiator.
- the coating composition of the present invention may include any effective amount of the polymerization initiator.
- the coating composition of the present invention includes from about 0.1 weight percent to about 5 weight percent of the polymerization initiator.
- the coating composition may be diluted with a suitable solvent, e.g. methylethylketone (MEK),
- MEK methylethylketone
- NMP 1-methyl-2-pyrrolidone
- DMF dimethylformamide
- PM propyleneglycol monomethyl-ether acetate
- DMSO dimethylsulfoxide
- additives known in the art e.g. leveling agents, surfactants (a nonionic fluorinated alkyl ether known as FC-430 available from 3M has been found to be a particularly suitable surfactant for use in the coating composition of the present invention), and wetting agents may be added to the coating composition in accord with the demands of the particular
- the coating composition of the present invention may be applied to the silaceous substrate by
- the coating composition of the present invention may by applied to optical fiber by
- the coating composition may be diluted using the above listed solvents to a solution suitable for application in a coating die, i.e. to a solids level, e.g. from about 50 weight percent solids to about 70 weight percent solids, sufficient to allow application of a coating layer having a thickness between about 5 microns and 10 microns on an exemplary 200 micron diameter fiber in one pass.
- a solids level e.g. from about 50 weight percent solids to about 70 weight percent solids
- composition was diluted with solvent, applied to microscope slides and cured.
- Soda-lime silica microscope slides (nominally 1" ⁇ 3" ⁇ 0.04") were visually inspected for flaws, e.g. nicks, scratches. Slides exhibiting visually
- coated slides were cured as noted in the tabulated results, i.e. by exposure to elevated
- the coated slides to be heat cured were placed on a rack and cured by heating in an oven for a particular length of time at a particular temperature.
- the specific cure conditions for each heat cured sample tested are set forth in the TABLES of results.
- the coated slides to be UV cured were aligned in a rack and cured by passing the rack under a FUSION
- the slides were subjected to UV radiation at an
- coated slides were either stored under ambient conditions or soaked in distilled water overnight prior to testing, as noted in the results given below.
- testing apparatus using a 4 point bend flexural test fixture with a span ratio of 2 and a crosshead speed of 0.2 in/min with the flawed side of the slide in tension.
- the strength enhancement (S.E.) ratio is a
- Examples 1 - 5 the strength enhancement provided by various coating compositions is determined using coated glass microscope slides, according to the procedure described above. To date, no strength enhancement data has been obtained regarding the preformance of the maleimide coatings of the present invention as strength enhancing coatings on thermally resistant optical fibers. However, in preliminary work with polyimide coatings, strength enhancement data obtained with coated optical fibers have shown a strong positive correlation with strength enhancement data obtained with coated microscope slides and it appears that strength enhancement results obtained with coated mircroscope slides may be used as a basis for reliable qualitative predictions regarding strength enhancement results on optical fibers.
- compositions were prepared for testing.
- the compositions were each diluted with NMP (to 30 percent solids), curtain coated on glass slides, heat cured and tested under ambient and high humidity conditions.
- compositions 1 - 3 were also diluted to 30 percent solids in NMP, coated on slides, cured and tested as above, and, in addition, the cured samples were
- compositions 4 - 8 were each diluted with MEK (to 30 percent solids), coated on microscope slides, cured by exposure to UV radiation and tested under ambient conditions. The number of samples tested(n), cure conditions (expressed as number of passes by UV
- bismaleimide coating compositions may be photocured and that the photocured coatings provide an improvement in S.E. ratio of about 20 percent under ambient conditions.
- a coating composition was prepared:
- Composition 9 was diluted with MEK to 30 percent
- compositions 16 - 22 are analogous to Compositions 4 and 10 - 15 described above, except that N,
- N'-(4,4'-diphenylmethane) bismaleimide was substituted for 2,2 bis [4-(4 maleimidophenoxy) phenyl] propane.
- compositions 4 and 10 - 22 were diluted to 30 percent solids with solvent (MEK was used as the solvent for
- compositions 4 and 10 - 15 NMP was used as the solvent for Compositions 16 - 22), coated on microscope slides, heat cured and tested under ambient conditions. The number of samples tested(n), cure conditions, coating thickness, mean stress at break, and S.E. ratio for each composition tested are set forth in TABLE 5.
- compositions 12 and 23 were diluted to 30 percent solids with MEK, applied to microscope slides, heat cured and tested under ambient conditions.
- An optical fiber (of nominal 200 micron diameter) was coated with a layer of composition number 24
- thermally resistant optical fiber comprising an 8 micron cured coating layer.
- Cure conditions were: 8" oven at 200°C; UV treatment with one 300 watt Fusion "H” bulb lamp; 2 foot cure oven at 350°C.
- a portion of the thermally resistant optical fiber (a 2.0512 mg sample) was subjected to
- Results of the analysis are given in the FIGURE as the weight of sample remaining, expressed as a percentage of the original sample weight, versus temperature.
- the coating layer exhibited very good thermal stability up to a temperature of about 400°C, with the sample weight then decreasing at a slow rate up to a pronounced drop off between about 550°C and
- thermally resistant optical fiber could potentially be applied in applications which require continued exposure to temperatures up to about 400°C, and would be able to tolerate brief excursions up to about 500°C.
- COMPOSITION STRESS RATIO CURE CONDITIONS (microns) CONDITIONS uncoated 10 12708 1.00 - - - - - - - - - Ambient
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Abstract
A thermally resistant article includes a silaceous substrate and a coating layer on the substrate wherein the coating layer is formed by the cured reaction product of a maleimide compound having at least two maleimide functional groups per molecule. A method for enhancing the strength of a silaceous substrate includes applying a layer of a maleimide coating composition to the core and cross-linking the coating composition to form a strength enhancing coating layer on the core.
Description
THERMALLY RESISTANT GLASS ARTICLE
TECHNICAL FIELD
The present invention relates to strength
enhancement of silaceous substrates and more
particularly to strength enhancement of silaceous optical fibers under high temperature conditions.
BACKGROUND OF THE INVENTION
Optical fibers include a small diameter fiber core having an index of refraction such that incident light may be internally reflected within the fiber core and thereby transmitted along the length of the fiber core. Typically, optical fiber cores are made from a brittle material, e.g. quartz or aluminosilicate glass. In order to enhance the strength of the
brittle, small diameter optical fiber core and to avoid damage to the surface of the fiber core, a coating layer is typically applied onto the surface of the fiber core using, e.g. nylon, polyethylene,
polyurethane, epoxy, silicone or acrylate coating compositions.
The performance of conventional optical fiber coating compositions is inadequate at temperatures greater than about 300 F and therefore limits the temperature range within which such optical fibers may be used.
SUMMARY OF THE INVENTION
A thermally resistant article is disclosed. The thermally resistant optical fiber comprises a silaceous substrate and a coating layer on the substrate. The coating layer comprises the cured reaction product of a reactive coating composition. The reactive coating composition comprises a maleimide compound having at least one and preferably two maleimide functional groups per molecule. The thermally resistant article exhibits improved strength at elevated temperatures, is suitable for continuous use at temperatures up to about 400°C and is tolerant of brief excursions up to about 500°C.
In a preferred embodiment, the silaceous substrate is selected from the group consisting of glasses, glass ceramics, silaceous ceramic materials and combinations thereof.
In a preferred embodiment, the coating composition comprises a mixture of a maleimide compound having at least two maleimide functional groups per molecule and a silane coupling agent.
In a preferred embodiment, the coating composition comprises a mixture of a maleimide compound having at least two maleimide functional groups per molecule and a comonomer.
In a preferred embodiment, the thermally resistant article comprises an optical fiber.
A method for enhancing the strength of a silaceous substrate is also disclosed. The method includes applying a layer of a coating composition to the
silaceous substrate wherein the coating composition comprises a maleimide compound having at least two maleimide functional groups per molecule and cross linking the coating composition to form a strength enhancing coating layer on the core.
BRIEF DESCRIPTION OF THE DRAWING:
The FIGURE shows a plot of the weight (expressed as a percentage of original weight) of a sample of a thermally resistant optical fiber of the present invention versus temperature.
DETAILED DESCRIPTION OF THE INVENTION
The thermally resistant article of the present invention includes a silaceous substrate and a strength enhancing coating layer on the substrate.
The silaceous substrate of the article of the present invention may comprise any silica-containing material, e.g. any glass, glass-ceramic, silaceous ceramic or combination thereof. Specific examples of suitable silaceous substrate materials include
borosilicate glass, silica, lithium aluminosilicate, KF glasses, and SSe glasses.
While the present invention is specifically described herein by reference to the preferred
embodiment of an optical fiber, it will be appreciated by one skilled in the art that the coating composition and process set forth herein may be used to increase the tensile and/or flexural strength of any silaceous substrate to provide strength enhanced elavated
temperature resistant articles other than optical fibers. For example, the coating compositions set forth herein may be used as an adhesive in glass/glass or glass/metal laminates, as a molding compound or as an encapsulant.
The coating layer is the cured reaction product of a reactive coating composition. The reactive coating composition includes a maleimide compound.
The maleimide compound of the coating composition of the present invention may be any compound which includes at least two reactive maleimide functional groups per molecule. The coating composition may include a mixture of maleimide compounds.
For example, the maleimide compound may be any maleimide compound according to the structural formula:
R1 and R2 independently are hydrogen or lower
(C1 to C4) alkyl;
R3 is an organic linking group that lacks any functional groups that would interfere with preparation of the maleimide groups or with the reactivity of the maleimide groups formed;
n = 1 ; and
m = 2 if n = 1, or m≥ 1 if n ≥1.
Preferably R1 and R2 are each hydrogen or
methyl. Most preferably, R1 and R2 are each
hydrogen.
R3 may be, e.g. an alkyl, cycloalkyl, aryl or aralkyl group and may be bonded to the maleimide groups through an oxygen atom.
Oligomeric polyfunctional maleimides, wherein n >
1 are suitable as the maleimide compound. Preferably,
the oligomeric polyfunctional maleimide is of
relatively low molecular weight, i.e. wherein n is greater than 1 but less than about 10. An exemplary oligomeric polyfunctional maleimide is known as Thermax MP-2000X, is commercially available from Kennedy and Klim, Inc. of Little Silver, New Jersey and has the structural formula:
Ml is a maleimide functional group, and
R4 is either H or CH3.
Preferably, the maleimide compound is a monomeric bismaleimide compound, i.e. any compound according to formula (1) above in which n = 1 and m = 2.
Suitable bismaleimides may be prepared, e.g. by reaction of maleic anhydride with a suitable diamine.
Examples of suitable diamines include aromatic
diamines, e.g. 4,4'- , 2,4'-, 3,3'- and 2,2'- diaminophenylmethane, aliphatic diamines, e.g. hexa- methylenediamine, dodecamethylenediamine,
cycloaliphatic diamines, e.g. 1,4
eyelohexylmethanediamine, 3,3'-, 4,4'- 2,4' and 2,2' dicyclohexylmethanediamines and aralkyldiamines, e.g. xylylenediamine. Other suitable diamines for use in
preparing bismaleimides include 4,4' diaminophenyl oxide, 1,3-bis [3-aminophenoxy] benzene, 2,2'-,
2,4'- 3,3'-, 4,4'- diaminobenzo-phenone.
Examples of suitable bismaleimide compounds include N,N' ethylenedimaleimide, N,N' -hexamethylenedimaleimide, N,N'
dodoecamethylenedimaleimide, 2,2 - bis [4 - (4 -maleimide phenoxy) phenyl] propane, N,N' - (4,4
diphenylmethane) bismaleimide, N,N' - 4 methyl - 1,3 -phenylene) bismaleimide, 6 - maleimido - 1 - (4' -maleimidophenyl) - 1,3,3 - trimethyl-indone, N,N' - o -phenylene - bismaleimide and N,N' p - phenylene
bismaleimide, N,N' m phenylene bismaleimide, N,N' - (oxy - p - phenylene) dimaleimide, N,N' methylene - p -phenylene) - dimaleimide, N,N' - 2,4 -tolylenedimaleimide, N,N' - p - xylene dimaleimide, N,N' oxydipropylenedimaleimide, N,N'
phenylethylenedimaleimide and N,N'
phenylpropylenedimaleimide.
The coating composition of the present invention may include from about 40 weight percent to about 99.5 weight percent of the maleimide compound. Preferably, the coating composition includes from about 60 weight percent to about 95 weight percent of the maleimide compound.
The maleimide compound may be the sole
polymerizable compound in the reactive coating
composition. Alternatively, the reactive coating composition may include a comonomer. Suitable
comonomers include any monomeric species which may be copolymerized with the maleimide compound, e.g. epoxy resins, monomers having reactive acetylenically
unsaturated or ethylenically unsaturated functional groups, oxazolines and monomers capable of undergoing Michael addition reactions.
Preferably, the comonomer is a multifunctional comonomer to provide a highly crosslinked cured
copolymeric coating layer.
A suitable epoxy resin comonomer is any monomeric or oligomeric compound which includes at least one epoxy, i.e. oxirane, functional group per molecule. Specific examples of epoxy compounds suitable as comonomers in the coating of the present invention include the diglycidyl ether of bisphenol A (such as EPON resins from Shell); glycidylethers of phenol or cresol-formaldehyde resins (e.g., epoxy novolac
oligomers such as DOW DEN resins); cycloaliphatic monomers such as 1, 4-vinylcyclohexene dioxide,
3-4-epoxycyclohexylmethyl-3, 4-epoxy-cyclohexane carboxylate; aromatic glycidyl amine resins such as glycidyl-p-aminophenol,
N,N,N;N'-tetraglycidyl-4,4'-methylene
bis(diaminobenzene), triglycidyl isocyanurate;
aliphatic glycidyl ethers such as trimethylolpropane triglycidylether and neopentyl glycol diglycidyl ether.
Suitable comonomers having acetylenically or ethylenically unsaturated functional groups may be any monomeric compound having at least one acetylenically or ethylenically unsaturated functional group per molecule.
Examples of suitable unsaturated comonomers include acrylic acids as well as amides and esters derived therefrom, e.g. acrylic acid, methacrylic acid, methylmethacrylate, acrylamide,
triethyleneglycol dimethacrylate, 1,4-butanediol diacrylate, trimethylolpropanetriacrylate and
1,3-Butylene glycol dimethacrylate. Also included are unsaturated materials such as, styrene,
n-vinylpyrrolidone and maleate esters. Unsaturated comonomers having multiple unsaturated sites are preferred.
Diallyl and divinyl compounds have been found to be particularly suitable ethylenically unsaturated comonomers. Examples of suitable diallyl and divinyl compounds include diallyl phthalate,
N,N'-diallyltartardiamide, 1,3 divinyltetra-methyldisiloxane,
3 ,9-divinyl-2,4,8,10-tetraoxaspiro[5,5] undecane, diallyl maleimide, 1,3 diallyl urea, and diallyl-carbonate.
Suitable oxazoline comonomers include 2 - methyl oxazoline and bis (2 - oxazolinyl) methane.
Suitable comonomers which are capable of
undergoing Michael addition reaction include primary amino compounds and thiol compounds. Specific and preferred examples include 3,3' diaminodiphenylsulfone and dicarboxylic acid dihydrazides, 1,4 - bis
(4-aminophenoxy) benzene; oxydianiline; bis
(p-aminocyclohexyl) methane and
4,4'-diaminophenylmethane.
The coating composition of the present invention may include from about 0 weight percent to about 60 weight percent of the comonomer. Preferably, the coating composition includes from about 5 weight percent to about 30 weight percent of the comonomer.
The reactive coating composition may include a silane coupling agent. Silane coupling agents suitable for use in the coating composition of the present invention include any organosilane monomer having one or more groups capable of reacting with the silaceous substrate and a nonhydrolyzable organic functional group capable of undergoing reaction to form a chemical bond with the maleimide compound described above.
Suitable organosilane coupling agents are those of the general formula:
wherein:
R4 is a nonhydrolyzable organic functional group which is capable of reacting with a
maleimide functional group, e.g.
(meth)acryloxyalkyl, vinyl, allyl, glyeidoxyalkyl or aminoalkyl, mercaptan;
R5 is a nonhydrolyzable nonfunctional
organic group, e.g. alkyl;
X is a hydroxyl group or hydrolyzable group, e.g. alkoxy, acetoxy, amino or halo; and
n = 0, 1 or 2.
The hydroxyl or hydrolyzable group X is capable of undergoing reaction with, or of undergoing hydrolysis and subsequent reaction with, silanol groups on the silaceous substrate to chemically bond the organosilane monomer to the surface of the substrate. The
nonhydrolyzable organic functional group is capable of undergoing reaction with the maleimide or with the comonomer of the coating composition to chemically bond the organosilane monomer within the cured coating layer. Respective reactions between the hydroxyl or hydrolyzable group X and the silaceous substrate and between the functional group R and the reactive
maleimide compound or a comonomer of the coating composition provide a chemical bonding between the cured coating layer and the silaceous substrate.
Preferably, n = 0 or 1, the organic functional group R is a group capable of undergoing free radical or cationic polymerization and the hydrolyzable group X
is alkoxy. Most preferably, n = 0 and the organic functional group R is (meth)acryloxyalkyl,
glycidoxyalkyl or aminoalkyl, and the hydrolyzable group X is methoxy or ethoxy. Specific examples of suitable organosilane coupling agents include
3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)aeryloxypropyltriethoxysilane, 3-(meth)-acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldichlorosilane, allyltrimethoxysilane,
vinylmethyldiethoxy-silane,
3-glycidoxypropyltrimethoxysilane,
3-aminopropyltrimeth-oxysilane and
p-aminophenyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
N-vinylbenzyl-N-2(trimethoxysily propyl amino ethyl) NH4Cl. Methacryloxypropyl- trimethoxysilane,
3-glycidoxypropyltrimethoxysilane and
aminophenyltrimethoxysilane are particularly preferred as the organosilane. Mixtures of two or more
organosilane coupling agents are also suitable as the organosilane coupling agent.
The coating composition of the present invention may include from about 0.5 weight percent to about 20 weight percent of the silane coupling agent.
Preferably, the coating composition includes from about 5 weight percent to about 15 weight percent silane coupling agent.
Maleimide coating compositions of the present invention which do not include a polymerization
initiator compound may be cured by heating to a
temperature of about 200°C to 300°C for a time
period of about 1-3 hours. Optionally, the coating composition may further comprise a polymerization initiator.
With the addition of a suitable polymerization initiator, the reactive maleimide coating composition may be cured by several different routes, i.e. the coating composition may be cured by photoinitiated free radial reactions, by thermally initiated free radical reactions, by cationic reactions, by Zwitterionic reactions, by cycloaddition reactions, by Michael addition reactions, by base catalyzed reactions and by combinations thereof.
Preferred photoinitiators of the coating
composition of the present invention are
photoinitiators which dissociate or decompose upon exposure to actinic radiation to yield a free radical. Conventional photosensitizing compounds may be used in combination with the photoinitiator. Photoinitiators which dissociate upon exposure to radiation having a wavelength in the range of 40 nm to 400 nm are
particularly preferred. Suitable photoinitiator compounds include, e.g. benzil, benzophenone,
camphorquinone, benzoin n-butyl ether, thioxanthone, 2-hydroxy-methyl-1-phenyl-propan-1-one,
1-hydroxycyclohexyl-phenylketone, isopropyl
thioxanthone, 2,2-dimethoxy-2-phenyl-2-benzyl-2-N-dimethylamino and 1- (4-morpholinophenyl-butanone). Preferred
photoinitiators include 2-hydroxy-methyl-1-phenyl-propan-1-one and 1-hydroxycyclohexylphenylketone.
The coating composition of the present invention may be heat cured by including a thermal initiator, e.g. a compound which decomposes upon heating to yield free radical, in the coating composition. The thermal initiator may be substituted for the photoinitiator to provide heat curable composition or may be included in addition to the photoinitiator to provide a composition that may be cured by exposure to heat and/or
radiation. Suitable thermal initiators include, e.g.
2, 2'-azobis (2, 4 dimethylvaleronitrile), 2-2'-azobis
(isobutyl-nitrile), 2, 2' azobis (methylbutylnitrile),
1, 1'-azobis (cyanocyclohexane) and mixtures thereof. 2, 2' azobis (isobutylnitrile) is preferred as the thermal initiator.
Alternatively, the coating composition of the present invention may be cured by a cationic reaction either thermally or photolytically, using a suitable acid initiator, e.g. onium salts, diazonium salts or
Lewis acids.
Alternatively, the coating composition of the present invention may be cured by thermal reactions
(which appear to be Zwitterionic in nature) by
including a compound having acid-base properties, e.g. an imidazole derivative, in the coating composition as a polymerization initiator.
Alternatively, the coating composition of the present invention may be cured by base catalyzed reactions by including a basic catalyst, e.g. a metal alkoxide, in the composition as a polymerization initiator.
Alternatively, the coating composition of the present invention may be cured by cycloaddition reaction if a triplet sensitizer or Lewis acid is included in the composition as a polymerization initiator.
The coating composition of the present invention may include any effective amount of the polymerization initiator. Preferably, the coating composition of the present invention includes from about 0.1 weight percent to about 5 weight percent of the polymerization initiator.
The coating composition may be diluted with a suitable solvent, e.g. methylethylketone (MEK),
1-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), a propyleneglycol monomethyl-ether acetate (PM), ethyl lactate or dimethylsulfoxide (DMSO).
Various additives known in the art, e.g. leveling agents, surfactants (a nonionic fluorinated alkyl ether known as FC-430 available from 3M has been found to be a particularly suitable surfactant for use in the coating composition of the present invention), and wetting agents may be added to the coating composition in accord with the demands of the particular
application method.
The coating composition of the present invention may be applied to the silaceous substrate by
conventional methods, e.g. dipping, spraying, rolling, curtain-coating.
In a preferred embodiment of the present
invention, the coating composition of the present invention may by applied to optical fiber by
conventional methods, i.e. by use of a conventional coating die. Significantly, the coating composition may be diluted using the above listed solvents to a solution suitable for application in a coating die, i.e. to a solids level, e.g. from about 50 weight percent solids to about 70 weight percent solids, sufficient to allow application of a coating layer having a thickness between about 5 microns and 10 microns on an exemplary 200 micron diameter fiber in one pass.
E X A M P L E S
A. EXAMPLES 1 - 5: GENERAL PROCEDURE
Testing of the coating compositions set forth in EXAMPLES 1- 5 was carried out in accord with the procedure set forth below. Particular conditions and exceptions to the procedure are noted in the EXAMPLES.
Each composition was diluted with solvent, applied to microscope slides and cured.
Soda-lime silica microscope slides (nominally 1" × 3" × 0.04") were visually inspected for flaws, e.g. nicks, scratches. Slides exhibiting visually
detectable flaws were discarded. The thickness of each of the remaining slides were recorded. One side of each of the slides was then abraded with 60 mesh grit at about 80 psi. The abraded slides were then soaked in distilled water for 24 hours, allowed to dry in air at ambient temperature and then heat treated in an oven at 600°C for 1 hour. The heat treated slides were stored in a dessicator.
Slides were removed from the dessicator and curtain coated with a solution of coating composition. The coated slides were, hung vertically in air for approximately 10 minutes and the excess was blotted from the bottom edge a second time.
The coated slides were cured as noted in the tabulated results, i.e. by exposure to elevated
temperature, by exposure to UV radiation or by a combination thereof.
The coated slides to be heat cured were placed on a rack and cured by heating in an oven for a particular length of time at a particular temperature. The specific cure conditions for each heat cured sample tested are set forth in the TABLES of results.
The coated slides to be UV cured were aligned in a rack and cured by passing the rack under a FUSION
SYSTEMS 300 WPI "H bulb" high pressure mercury lamp. The flawed side of each slide was alternately oriented upwardly and downwardly with the successive passes.
The slides were subjected to UV radiation at an
intensity of about 900 mW/cm2 for 5-6 seconds per pass. The number of passes required to obtain a
tackfree coating was recorded for each side.
The coated slides were either stored under ambient conditions or soaked in distilled water overnight prior to testing, as noted in the results given below.
The slides were tested with an INSTRON 1122
testing apparatus using a 4 point bend flexural test fixture with a span ratio of 2 and a crosshead speed of 0.2 in/min with the flawed side of the slide in tension.
The strength enhancement (S.E.) ratio is a
quantity indicative of the improved flexural strength imparted to the silaceous substrate by the strength enhancing coating layer of the present invention and is determined by comparing results obtained with coated slides and those obtained with noncoated slides under the same test conditions. "Ambient" strength
enhancement values were derived by testing coated slides that had been stored under ambient conditions and tested under ambient conditions. "High Humidity" strength enhancement values were derived by testing coated slides that had been stored submerged overnight in water and tested wet at room temperature.
B. EXAMPLES 1 - 5 CORRELATION OF RESULTS OBTAINED
WITH COATED MICROSCOPE SLIDES TO PREDICTED RESULTS WITH COATED OPTICAL FIBERS
In Examples 1 - 5 below, the strength enhancement provided by various coating compositions is determined using coated glass microscope slides, according to the procedure described above. To date, no strength enhancement data has been obtained regarding the preformance of the maleimide coatings of the present invention as strength enhancing coatings on thermally resistant optical fibers. However, in preliminary work with polyimide coatings, strength enhancement data obtained with coated optical fibers have shown a strong positive correlation with strength enhancement data obtained with coated microscope slides and it appears that strength enhancement results obtained with coated mircroscope slides may be used as a basis for reliable qualitative predictions regarding strength enhancement results on optical fibers. In the results presented in EXAMPLES 1 - 5 below, a high strength enhancement ratio with a particular coating composition on a microscope slide may be interpreted as an indication that a high strength enhancement ratio would likely be obtained with an analogous coated optical fiber and a low strength enhancement ratio for a particular coating composition on a microscope slide would indicate that a low strength enhancement ratio would likely be obtained with an analogous coated optical fiber.
EXAMPLE 1
The following bismaleimide coating compositions were prepared:
COMPOSITION 1 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 70
2,4 ethylmethylimidazole 0.8 diglycidyl ether of bisphenol A 18
3-glycidoxypropyltrimethoxysilane 11 surfactant (FC-430, 3M) 0.2
COMPOSITION 2 WEIGHT PERCENT
2-2-bis [4-(4-maleimidophenoxy)
phenyl] propane 87
2,4-ethylmethylimidazole 2
3,-glycidoxypropyltrimethoxysilane 10 surfactant (FC-430, 3M) 1.0
COMPOSITION 3 WEIGHT PERCENT
2-2-bis [4-(4-maleimidophenoxy)
phenyl] propane 89.7 3,-glycidoxypropyltrimethoxysilane 10 surfactant (FC-430) (3M) 0.3
Coated samples were prepared for testing. The compositions were each diluted with NMP (to 30 percent solids), curtain coated on glass slides, heat cured and tested under ambient and high humidity conditions.
The number of samples tested(n), cure conditions, coating thickness, test conditions, mean stress at break and S.E. ratio are set forth in TABLE 1.
The results presented in TABLE 1 show that the coating compositions tested provided very significant improvements in S.E. ratio, i.e. an increase by a
factor of about 2 under both ambient and high humidity testing conditions.
Compositions 1 - 3 were also diluted to 30 percent solids in NMP, coated on slides, cured and tested as above, and, in addition, the cured samples were
subjected to heat ageing under high temperature
conditions (350°C) prior to testing. The number of samples tested(n), cure and heat ageing conditions, coating thickness, test conditions, mean stress at break and S.E. ratio obtained for each composition tested are set forth in TABLE 2.
The results presented in TABLE 2 show that coating compositions tested provided improved S.E. ratio after high temperature ageing under ambient conditions, but that the S.E. ratio dropped significantly when the heat aged samples were tested under high humidity conditions.
EXAMPLE 2
The following bismaleimide coating compositions were prepared: COMPOSITION 4 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 90
3-glycidoxypropyltrimethoxysilane 10
COMPOSITION 5 WEIGHT PERCENT 2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 77
3-glycidoxypropyltrimethoxysilane 13 acetophenone 10
EXAMPLE 2 ( Cont ' d . )
COMPOSITION 6 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 77 benzophenone 10
3-glycidoxypropyltrimethoxysilane 13
COMPOSITION 7 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 77
2-hydroxy-2-methyl-1-phenyl-propan-1-one 10
3-glycidoxypropyltrimethoxysilane 13
COMPOSITION 8 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 67
3-glycidoxypropyltrimethoxysilane 13
2-hydroxy-2-methyl-1-phenyl-propan-1-one 20
Coated samples were prepared and tested.
Compositions 4 - 8 were each diluted with MEK (to 30 percent solids), coated on microscope slides, cured by exposure to UV radiation and tested under ambient conditions. The number of samples tested(n), cure conditions (expressed as number of passes by UV
source), coating thickness, mean stress at break and S.E. ratio for each composition tested are set forth in TABLE 3.
The results presented in TABLE 3 show that
bismaleimide coating compositions may be photocured and that the photocured coatings provide an improvement in S.E. ratio of about 20 percent under ambient conditions.
EXAMPLE 3
A coating composition was prepared:
COMPOSITION 9 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 84
3-glycidoxypropyltrimethoxysilane 13 triarylsulfoniumhexafluoroantimonate 3
(UVI 6974, Union Carbide)
Coated samples were prepared and tested.
Composition 9 was diluted with MEK to 30 percent
solids, coated on microscope slides, UV cured,
thermally post-cured and tested under ambient
conditions. The number of samples tested(n), UV cure conditions (expressed as number of passes by UV
source), thermal post cure conditions, coating
thickness, mean stress at break and S.E. ratio for each composition tested are set forth in TABLE 4.
The results presented in TABLE 4 show that a thermal post cure of 1 - 3 hours at 200°C increased the S.E. ratio of a photocured coating layer from about 1.2 to about 1.9. Further post cure, i.e. 4 hours at 200 C resulted in a decrease in S.E. ratio from about 1.9 to about 1.8. The results suggest that exposure to UV radiation alone is not sufficient to fully cure coating composition 9.
EXAMPLE 4
The following bismaleimide coating compositions were prepared.
COMPOSITION 10 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60 diallyl maleate 30
3-glycidoxypropyltrimethoxysilane 10
COMPOSITION 11 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60 diallyl urea 30
3-glycidoxypropyltrimethoxysilane 10
COMPOSITION 12 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60 diallyl carbonate 30
3-glycidoxypropyltrimethoxysilane 10
COMPOSITION 13 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60 diallyl phthalate 30
3-glycidoxypropyltrimethoxysilane 10
COMPOSITION 14 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60
N,N'-diallyltartardiamide 30
3-glycidoxypropyltrimethoxysilane 10
EXAMPLE 4 (Cont ' d . )
COMPOSITION 15 WEIGHT PERCENT
2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60
3,9-divinyl-2,4,8,10
tetraoxaspiro[5,5] undecane 30
3-glycidoxyproρyltrimethoxysilane 10
COMPOSITIONS 16 - 22
Compositions 16 - 22 are analogous to Compositions 4 and 10 - 15 described above, except that N,
N'-(4,4'-diphenylmethane) bismaleimide was substituted for 2,2 bis [4-(4 maleimidophenoxy) phenyl] propane.
Coated samples were prepared and tested.
Compositions 4 and 10 - 22 were diluted to 30 percent solids with solvent (MEK was used as the solvent for
Compositions 4 and 10 - 15, NMP was used as the solvent for Compositions 16 - 22), coated on microscope slides, heat cured and tested under ambient conditions. The number of samples tested(n), cure conditions, coating thickness, mean stress at break, and S.E. ratio for each composition tested are set forth in TABLE 5.
EXAMPLE 5
The following example again uses composition 15 which is repeated below.
COMPOSITION 15 WEIGHT PERCENT 2,2-bis [4-(4-maleimidophenoxy)
phenyl] propane 60
3,9-divinyl-2,4,8,10
tetraoxaspiro[5,5]undecane 30
3-glycidoxypropyltrimethoxysilane 10 Coated samples were prepared and tested.
Compositions 12 and 23 were diluted to 30 percent solids with MEK, applied to microscope slides, heat cured and tested under ambient conditions. In
addition, several cured samples were subjected to further heat ageing after cure and prior to testing.
The number of samples tested(n), cure conditions, heat ageing conditions, test conditions, mean stress at break and S.E. ratio for each composition tested are set forth in TABLE 6.
The results presented in TABLES 5 - 6 show that flexibilizing comonomers copolymerized with 2,2-bis
[4-(4-maleimidophenoxy) phenyl] propane, did not
negatively affect the S.E. ratio of heat aged samples, but copolymerization of flexibilizing monomers with N,N'-(4,4'-diphenylmethane) bismaleimide adversely affected the S.E. ratio provided by the coatings.
EXAMPLE 6
An optical fiber (of nominal 200 micron diameter) was coated with a layer of composition number 24
(applied as a 54% solution in MEK) and cured by UV and thermal to provide a thermally resistant optical fiber comprising an 8 micron cured coating layer. Cure conditions were: 8" oven at 200°C; UV treatment with one 300 watt Fusion "H" bulb lamp; 2 foot cure oven at 350°C. A portion of the thermally resistant optical fiber (a 2.0512 mg sample) was subjected to
thermogravimetric analysis at a heating rate of
40°C/minute. Results of the analysis are given in the FIGURE as the weight of sample remaining, expressed as a percentage of the original sample weight, versus temperature.
The coating layer exhibited very good thermal stability up to a temperature of about 400°C, with the sample weight then decreasing at a slow rate up to a pronounced drop off between about 550°C and
620°C. Based on this preliminary analysis, it would appear that the thermally resistant optical fiber could potentially be applied in applications which require continued exposure to temperatures up to about 400°C, and would be able to tolerate brief excursions up to about 500°C.
COMPOSITION 24 Weight Percent
2-2-bis [4-(4-maleimidophenoxy)
phenyl] propane 70 diglycidyl ether of bisphenol A 17
2,4-ethylmethylimidazole 1
2-hydroxy-2-methyl-1-phenyl-propan-1-one 1
3-glycidoxy propyl trimethoxysilane 11
TABLE 1
COATING MEAN S.E. THICKNESS TEST
COMPOSITION n STRESS RATIO CURE CONDITIONS (microns) CONDITIONS noncoated 7 12720 1.00 - - - - - - - - - - - - AMBIENT
1 8 26900 2.11 90' @ 90°C + 2h @ 225°C 28.9 AMBIENT
2 12 24720 1.94 90' @ 90°C + 2h @ 225°C 39.7 AMBIENT noncoated 10 12940 1.00 - - - - - - - - - - - - AMBIENT
3 10 27230 2.10 60' @ 80°C + 4h @ 200°C 24.9 AMBIENT noncoated 8 11560 1.00 - - - - - - - - - - - - HIGH
HUMIDITY
3 8 22580 1.95 60' @ 80°C + 4h @ 200°C - - - - HIGH
HUMIDITY
TABLE 2
HIGH TEMPERATURE STABILITY
COATING
COATING n MEAN S.E. THICKNESS TEST COMPOSITION STRESS RATIO CURE CONDITIONS (microns) CONDITIONS noncoated 11 12600 1.00 - - - - - - - - AMBIENT
1 13 23450 1.86 1h @ 100°C + 1h @ 200°C 11.2 AMBIENT
2 8 19550 1.55 1h @ 100ºC + 1h @ 200°C 24.4 AMBIENT
3 9 24990 1.98 1h @ 100°C + 1h @ 200°C 14.8 AMBIENT noncoated 13 12570 1.00 1h @ 350°C AMBIENT
1 11 17880 1.42 1h @ 100°C + 1h @ 200° 30.3 AMBIENT
+ 1h @ 350°C
2 12 20430 1.63 1h @ 100°C + 1h @ 200°C 24.6 AMBIENT
+ 1h @ 350°C
3 9 21510 1.71 1h @ 100°C + 1h @ 200°C 22.9 AMBIENT
+ 1h @ 350°C
noncoated 9 11690 1.00 - - - - HIGH HUMIDITY
1 8 19610 1.68 1h @ 100°C + 1h @ 200°C HIGH HUMIDITY
2 7 18660 1.60 1h @ 100°C + 1h @ 200°C HIGH HUMIDITY
3 10 20590 1.76 1h @ 100°C + 1h @ 200°C HIGH HUMIDITY noncoated 10 11280 1.00 1h @ 350°C - - - - HIGH HUMIDITY
TABLE 2 (Continued)
HIGH TEMPERATURE STABILITY
COATING
COATING n MEAN S.E. THICKNESS TEST
COMPOSITION STRESS RATIO CURE CONDITIONS (microns) CONDITIONS
1 10 13850 1.23 1h @ 100°C + 1h @ 200°C coating HIGH HUMIDITY
+ 1h @ 350°C peeled
2 10 13150 1.17 1h @ 100°C + 1h @ 200°C coating HIGH HUMIDITY
+ 1h @ 350°C peeled
3 10 13220 1.17 1h @ 100°C + 1h @ 200°C coating HIGH HUMIDITY
+ 1h @ 350°C peeled
TABLE 3
COATING
COATING MEAN SE CURE THICKNESS COMPOSITION n STRESS RATIO CONDITIONS (microns) noncoated 12 13131 1.00 - - - - - - - -
4 11 15815 1.20 15/1 X 40.1 noncoated 12 12895 1.00 - - - - - - - -
5 10 15261 1.18 7/2 X 44.2
6 11 15045 1.17 5/1 X 27.9
7 12 15842 1.23 3/2 X 57.2
8 11 14486 1.14 1 X 29.4
TABLE 4
COATING
COATING n MEAN SE THICKNESS TEST
COMPOSITION STRESS RATIO CURE CONDITIONS (microns) CONDITIONS uncoated 10 12708 1.00 - - - - - - - - Ambient
9 11 15646 1.23 7 X 45.2 Ambient
9 11 24476 1.93 7X + 1h @ 200°C 31.8 Ambient
9 11 24310 1.91 7X + 2h @ 200°C 22.0 Ambient
9 8 24175 1.90 7X + 3h @ 200°C 29.8 Ambient
9 10 22449 1.77 7X + 4h @ 200°C 44.2 Ambient
TABLE 5
COATING
COATING n MEAN SE THICKNESS TEST
COMPOSITION STRESS RATIO CURE CONDITIONS (microns) CONDITIONS noncoated 13 13327 1.00 - - - - - - - - Ambient 4 9 26956 2.02 3h @ 200°C 52.9 Ambient
10 10 25923 1.95 3h @ 200°C 31.4 Ambient
11 10 23311 1.75 3h @ 200°C 15.2 Ambient
12 11 26209 1.97 3h @ 200°C 16.7 Ambient noncoated 9 13111 1.00 - - - - - - - - Ambient
13 11 25594 1.95 4.5h @ 200 300°C - - - - Ambient
14 11 17097 1.30 4.5h @ 200 300°C - - - - Ambient
15 10 24873 1.90 4.5h @ 200 300°C - - - - Ambient
20 11 19919 1.52 4.5h @ 200 300°C - - - - Ambient
21 12 19169 1.46 4.5h @ 200 300°C - - - - Ambient
22 11 18998 1.45 4.5h @ 200 300°C - - - - Ambient noncoated 13 13327 1.0 - - - - - - - - Ambient
16 11 24058 1.81 3h @ 200°C 4.1 Ambient
17 8 18944 1.42 3h @ 200°C 20.6 Ambient
18 11 20264 1.52 3h @ 200°C 13.0 Ambient
19 9 21708 1.63 3h @ 200°C 19.0 Ambient
TABLE 6
COATING MEAN SE TEST COMPOSITION STRESS RATIO CURE CONDITIONS CONDITIONS
uncoated 12 13596 1.00 - - - - Ambient
12 10 23885 1.76 1.5h @ 200°C Ambient
15 5 15433 1.14 1.5h @ 200°C Ambient
15 4 20545 1.51 3h @ 200°C Ambient
15 3 19423 1.43 4h @ 200°C Ambient
12 12 17899 1.32 1.5h @ 200°C + 1h @ 325°C Ambient
15 10 16882 1.24 1.5h @ 200°C + 1h @ 325°C Ambient
While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been
described by way of illustrations and not limitations.
What is claimed is:
Claims
CLAIM 1. A thermally resistant article, comprising: a silaceous substrate; and
a thermally resistant strength enhancing coating layer on the substrate, said layer comprising the cured reaction product of a reactive coating composition, said composition comprising a maleimide compound having at least one maleimide functional group per molecule.
CLAIM 2. The article of Claim 1, wherein said
substrate comprises a material selected from the group of glasses, glass-ceramics, silaceous ceramics and combinations thereof.
CLAIM 3. The article of Claim 1, wherein the article comprises a thermally resistant optical fiber and the substrate comprises a fiber core.
CLAIM 4. The article of Claim 3, wherein the fiber core is cylindrical and the coating layer
circumferentially surrounds the fiber core.
CLAIM 5. The article of Claim 1, wherein the maleimide a compound comprises a bismaleimide compound.
CLAIM 6. The article of Claim 1, wherein the maleimide compound is selected from the group consisting of N,N' ethylenedi-maleimide, N,N' - hexamethylenedimaleimide, N,N' dodoecamethylenedimaleimide, 2,2 - bis [4 - (4 -maleimidephenoxy) phenyl] proppne, N,N' - (4,4
diphenylmethane) bismaleimide, N,N' - 4 methyl - 1,3 -phenylene) bismaleimide, 6 - maleimido - 1 - (4' -maleimide-ophenyl) - 1,3,3 - trimethylindone, N,N' - o- phenylenediamine - bismaleimide and N,N' p -phenylene bismaleimide, N,N' m phenylene bismaleimide, N,N' - (oxy - p - phenylene) dimaleimide, N,N'
methylene - p - phenylene) - dimaleimide, N,N' - 2,4 -tolylenedimaleimide, N,N' - p - xylene dimaleimide, N,N' oxydipropylenedimaleimide, N,N'
phenylethylenedimaleimide and
N,N'-p-phenylpropylenedimaleimide.
CLAIM 7. The fiber of Claim 1, wherein the coating composition comprises a mixture of the maleimide compound and a silane coupling agent.
CLAIM 8. The article of Claim 7, wherein the silane coupling agent has at least one reactive
organofunctional group that is copolymerizable with the maleimide compound and at least two functional groups selected from the group consisting of hydride,
hydroxyl, hydrolyzable inorganic functional groups and hydrolyzable organic functional groups.
CLAIM 9. The article of Claim 8, wherein the silane coupling agent is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane,
aminophenyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyl (triethoxysilane),
N-vinylbenzyl-N-2(trimethoxysilylpropylaminoethylNH4Cl) and methacryloxypropyltrimethoxysilane.
CLAIM 10. The article of Claim 7, wherein the mixture comprises up to about 20 weight % silane coupling agent,
CLAIM 11. The article of Claim 1, wherein the coating composition comprises a mixture of the maleimide
compound and a comonomer capable of undergoing
copolymerization with the maleimide compound.
CLAIM 12. The article of Claim 11, wherein the
comonomer comprises an epoxy resin having at least one epoxy functional group per molecule.
CLAIM 13. The article of Claim 12, wherein the epoxy resin is selected from the group consisting of
diglycidylether of bisphenol A, polyglycidylether of cresol novolac resin and
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane
carboxylate.
CLAIM 14. The article of Claim 11, wherein the
comonomer comprises an acetylenically or ethylenically unsaturated compound having at least one unsaturated functional group per molecule.
CLAIM 15. The article of Claim 14, wherein the
ethylenically unsaturated compound is selected from the group consisting of diallyl phthalate,
N,N'-diallyltartardiamide, 1,3 divinyltetra-methyldisiloxane,
3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5] undecane, diallyl maleate, 1,3 diallyl urea, and
diallyl-carbonate.
CLAIM 16. The article of Claim 11, wherein the
comonomer comprises an oxazoline compound.
CLAIM 17. The article of Claim 16, wherein the
oxazoline compound is selected from the group
consisting of 2-methyl-oxazoline and
bis(2-oxazoliny1)methane.
CLAIM 18. The article of Claim 11, wherein the
comonomer comprises a compound capable of undergoing Michael addition reaction with the maleimide compound.
CLAIM 19. The article of Claim 18, wherein the
comonomer is selected from the group consisting of 3,3', diaminodiphenyl-sulfone and 1,4-bis(4
aminophenoxy)benzene.
CLAIM 20. The article of Claim 11, wherein the
comonomer comprises a silane coupling agent having at least one reactive organofunctional group that is copolymerizable with the maleimide compound and at least two functional groups selected from the group consisting of hydride, hydroxyl, hydrolyzable inorganic functional groups and hydrolyzable inorganic functional groups.
CLAIM 21. The article of Claim 11, wherein the silane coupling agent is selected from the group consisting of 3-glycidoxypropyl-trimethoxysilane, aminophenyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyl (triethoxysilane),
N-vinylbenzyl-N-2(trimethoxysilylpropylaminoethylNH4Cl) and methacryloxy-propyltrimethoxysilane.
CLAIM 22. The article of Claim 1, wherein the reactive coating composition further comprises a curing
initiator.
CLAIM 23. THe article of Claim 22, wherein the
initiator comprises a photoinitiator.
CLAIM 24. The article of Claim 22, wherein the
initiator is a cationic initiator.
CLAIM 25. The article of Claim 22, wherein the
initiator is a thermal initiator.
CLAIM 26. The article of Claim 11, wherein the coating composition comprises from about 50 parts by weight to about 100 parts by weight of the maleimide compound, from about 25 parts by weight to about 50 parts by weight comonomer, and
from about 5 parts of weight to about 15 parts by weight of a silane coupling agent.
CLAIM 27. A method for enhancing the strength of a silaceous substrate, comprising:
applying a layer of a temperature resistant, strength enhancing coating composition to the
substrate, said coating composition comprising a maleimide compound having at least two reactive
maleimide functional groups per molecule, and
cross linking the coating composition to form a coating layer on the core.
CLAIM 28. The method of Claim 27, wherein the substrate is selected from the group consisting of glasses, glass-ceramics, silaceous ceramic materials and
combinations thereof.
CLAIM 29. The method of Claim 27, wherein the silaceous substrate is an optical fiber core.
CLAIM 30. The method of Claim 29, wherein the fiber core is cylindrical and the coating layer
circumferentially surrounds the fiber core.
CLAIM 31. The method of Claim 26, wherein the coating composition comprises a mixture of the maleimide compound and a silane coupling agent.
CLAIM 32. The method of Claim 31, wherein the silane coupling agent has at least one reactive
organofunctional group that is copolymerizable with the maleimide compound and at least two functional groups selected from the group consisting of hydride,
hydroxyl, hydrolyzable inorganic functional groups and hydrolyzable organic functional groups.
CLAIM 33. The method of Claim 32, wherein the silane coupling agent is selected from the group consisting of 3-glycidoxypropyl-trimethoxysilane,
aminophenyltrimethoxysilane
2-(3,4-epoxycyclohexyl)ethyl (triethoxysilane),
N-vinylbenzyl-N-2(trimethoxysilylpropylaminoethylNH4Cl) and methacryloxy-propyltrimethoxysilane.
CLAIM 34. The method of Claim 31, wherein the mixture comprises up to about 20 weight % silane coupling agent.
CLAIM 35. The-method of Claim 27, wherein the coating composition comprises a mixture of the maleimide
compound and a comonomer capable of undergoing
copolymerization with the maleimide compound.
CLAIM 36. The method of Claim 35, wherein the comonomer comprises an epoxy resin having at least one epoxy functional per molecule.
CLAIM 37. The method of Claim 36, wherein the epoxy resin is selected from the group consisting of
diglycidylether of bisphenol A, polyglycidylether of cresol novolac resin and
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane
carboxylate.
CLAIM 38. The method of Claim 35, wherein the comonomer comprises an acetylenically or ethylenically
unsaturated compound having at least one unsaturated functional group per molecule.
CLAIM 39. The method of Claim 38, wherein the
ethylenically unsaturated compound is selected from the group consisting of diallyl phthalate,
N,N'-diallyltartardiamide, 1,3 divinyltetra-methyldisiloxane,
3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5] undecane, diallyl maleate, 1,3 diallyl urea, and
diallyl-carbonate.
CLAIM 40. The method of Claim 35, wherein the comonomer comprises an oxazoline compound.
CLAIM 41. The method of Claim 40, wherein the oxazoline compound is selected from the group consisting of
2-methyl-oxazoline and bis(2-oxazolinyl)methane.
CLAIM 42. The method of Claim 35, wherein the comonomer comprises a compound capable of undergoing Michael addition reaction with the maleimide compound.
CLAIM 43. The method of Claim 42, wherein the comonomer is selected from the group consisting of 3,3',
diaminodiphenyl-sulfone and
1,4-bis(4-aminoρhenoxy)benzene.
CLAIM 44. The method of Claim 35, wherein the comonomer comprises a silane coupling agent having at least one reactive organofunctional group that is copolymerizable with the maleimide compound and at least two functional groups selected from the group consisting of hydride, hydroxyl, hydrolyzable inorganic functional groups and hydrolyzable inorganic functional groups.
CLAIM 45. The method of Claim 44, wherein the silane coupling agent is selected from the group consisting of 3-glycidoxypropyl-trimethoxysilane,
aminophenyltrimethoxysilane
2-(3,4-epoxycyclohexyl)ethyl (triethoxysilane),
N-vinylbenzyl-N-2(trimethoxysilylpropylaminoethylNH4Cl) and methacryloxy-propyltrimethoxysilane.
CLAIM 46. The method of Claim 27, wherein the mixture further comprises a curing initiator.
CLAIM 47. The method of Claim 46, wherein the initiator comprises a photoinitiator.
CLAIM 48. The method of Claim 46, wherein the initiator is a cationic initiator.
CLAIM 49. The method of Claim 46, wherein the initiator is a thermal initiator.
CLAIM 50. The method of Claim 27, wherein the coating composition is cross linked by heating the coated substrate.
CLAIM 51. The method of Claim 27, wherein the coating composition is cross linked by irradiating the coated substrate.
CLAIM 52. The method of Claim 27, wherein the coating composition is crosslinked by cationic reaction.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU36112/93A AU3611293A (en) | 1992-06-16 | 1993-02-05 | Thermally resistant glass article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US89943692A | 1992-06-16 | 1992-06-16 | |
US899,436 | 1992-06-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993025386A1 true WO1993025386A1 (en) | 1993-12-23 |
Family
ID=25410970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/001031 WO1993025386A1 (en) | 1992-06-16 | 1993-02-05 | Thermally resistant glass article |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU3611293A (en) |
WO (1) | WO1993025386A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034194A (en) * | 1994-09-02 | 2000-03-07 | Quantum Materials/Dexter Corporation | Bismaleimide-divinyl adhesive compositions and uses therefor |
WO2000020517A2 (en) * | 1999-01-19 | 2000-04-13 | Dsm N.V. | Radiation-curable compositions comprising maleimide compounds and method for producing a substrate with a cured layer |
JP2002284751A (en) * | 2001-03-28 | 2002-10-03 | Nagase Kasei Kogyo Kk | New compound, and crosslinking agent for water- absorbing resin using the same and water-absorbing resin |
US6790597B2 (en) | 1994-09-02 | 2004-09-14 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
US6960636B2 (en) | 1994-09-02 | 2005-11-01 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
DE102007037622A1 (en) * | 2007-08-09 | 2009-02-12 | Siemens Ag | Resin formulation with cross-linkable bismaleimide-component, useful e.g. for manufacturing electrically isolating sealing compound, and foil comprises bismaleimide-component having bismaleimide phenylindane |
DE102007037621A1 (en) * | 2007-08-09 | 2009-02-12 | Siemens Ag | Bismaleimide-based resin formulation for producing a film, producing a film using the resin formulation and using the film |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5018828A (en) * | 1986-02-24 | 1991-05-28 | Mitsui Petrochemcial Industries, Ltd. | Optical fiber |
US5153288A (en) * | 1990-11-30 | 1992-10-06 | Toray Industries, Inc. | Cladding material for optical fiber and method for its manufacture |
-
1993
- 1993-02-05 WO PCT/US1993/001031 patent/WO1993025386A1/en active Application Filing
- 1993-02-05 AU AU36112/93A patent/AU3611293A/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5018828A (en) * | 1986-02-24 | 1991-05-28 | Mitsui Petrochemcial Industries, Ltd. | Optical fiber |
US5153288A (en) * | 1990-11-30 | 1992-10-06 | Toray Industries, Inc. | Cladding material for optical fiber and method for its manufacture |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034194A (en) * | 1994-09-02 | 2000-03-07 | Quantum Materials/Dexter Corporation | Bismaleimide-divinyl adhesive compositions and uses therefor |
US6790597B2 (en) | 1994-09-02 | 2004-09-14 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
US6825245B2 (en) | 1994-09-02 | 2004-11-30 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
US6916856B2 (en) | 1994-09-02 | 2005-07-12 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
US6960636B2 (en) | 1994-09-02 | 2005-11-01 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
WO2000020517A2 (en) * | 1999-01-19 | 2000-04-13 | Dsm N.V. | Radiation-curable compositions comprising maleimide compounds and method for producing a substrate with a cured layer |
WO2000020517A3 (en) * | 1999-01-19 | 2000-08-24 | Dsm Nv | Radiation-curable compositions comprising maleimide compounds and method for producing a substrate with a cured layer |
JP2002284751A (en) * | 2001-03-28 | 2002-10-03 | Nagase Kasei Kogyo Kk | New compound, and crosslinking agent for water- absorbing resin using the same and water-absorbing resin |
DE102007037622A1 (en) * | 2007-08-09 | 2009-02-12 | Siemens Ag | Resin formulation with cross-linkable bismaleimide-component, useful e.g. for manufacturing electrically isolating sealing compound, and foil comprises bismaleimide-component having bismaleimide phenylindane |
DE102007037621A1 (en) * | 2007-08-09 | 2009-02-12 | Siemens Ag | Bismaleimide-based resin formulation for producing a film, producing a film using the resin formulation and using the film |
DE102007037621B4 (en) * | 2007-08-09 | 2014-09-18 | Siemens Aktiengesellschaft | Use of a resin formulation as a film in a method for the planar contacting of an electrical contact point of an electrical component and a corresponding method |
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AU3611293A (en) | 1994-01-04 |
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