CN1507463A - 用于制备双极板的模塑组合物 - Google Patents
用于制备双极板的模塑组合物 Download PDFInfo
- Publication number
- CN1507463A CN1507463A CNA028095936A CN02809593A CN1507463A CN 1507463 A CN1507463 A CN 1507463A CN A028095936 A CNA028095936 A CN A028095936A CN 02809593 A CN02809593 A CN 02809593A CN 1507463 A CN1507463 A CN 1507463A
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- China
- Prior art keywords
- composition
- ester
- diacrylate
- weight
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 238000000465 moulding Methods 0.000 title abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- -1 acrylic ester Chemical class 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 5
- 229930003836 cresol Natural products 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical group C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001282 organosilanes Chemical class 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- LEHNQGSPRXHYRT-UHFFFAOYSA-N 2-dodecyl-1h-imidazole Chemical class CCCCCCCCCCCCC1=NC=CN1 LEHNQGSPRXHYRT-UHFFFAOYSA-N 0.000 claims description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical class CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims 2
- 229950007687 macrogol ester Drugs 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 239000002966 varnish Substances 0.000 claims 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 1
- 229940042596 viscoat Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000011231 conductive filler Substances 0.000 abstract description 6
- 238000001723 curing Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012765 fibrous filler Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003826 tablet Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
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- ZWUBFMWIQJSEQS-UHFFFAOYSA-N 1,1-bis(ethenyl)cyclohexane Chemical compound C=CC1(C=C)CCCCC1 ZWUBFMWIQJSEQS-UHFFFAOYSA-N 0.000 description 1
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- 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
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- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- SZCFDTYKNQJQKT-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC2OC2C1OCC1CO1 SZCFDTYKNQJQKT-UHFFFAOYSA-N 0.000 description 1
- XORJNZNCVGHBDZ-UHFFFAOYSA-N 2-[2-(6-oxabicyclo[3.1.0]hexan-2-yloxy)ethoxy]-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC2OC2C1OCCOC1C2OC2CC1 XORJNZNCVGHBDZ-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RXBBSTXUVVVWRC-UHFFFAOYSA-N 3-[3-[4,4-dimethyl-3-(oxiran-2-ylmethyl)-2,5-dioxoimidazolidin-1-yl]-2-(oxiran-2-ylmethoxy)propyl]-5,5-dimethyl-1-(oxiran-2-ylmethyl)imidazolidine-2,4-dione Chemical compound O=C1N(CC(CN2C(C(C)(C)N(CC3OC3)C2=O)=O)OCC2OC2)C(=O)C(C)(C)N1CC1CO1 RXBBSTXUVVVWRC-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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WXQZLPFNTPKVJM-UHFFFAOYSA-N 4-[(4-hydroxycyclohexyl)methyl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1CC1CCC(O)CC1 WXQZLPFNTPKVJM-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
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- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
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- OQAPYXJOOYQXDV-UHFFFAOYSA-N 5,5-dimethyl-3-[2-(oxiran-2-ylmethoxy)propyl]-1-(oxiran-2-ylmethyl)imidazolidine-2,4-dione Chemical compound C1OC1COC(C)CN(C(C1(C)C)=O)C(=O)N1CC1CO1 OQAPYXJOOYQXDV-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
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- 239000004971 Cross linker Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
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- JKVUNJFYNJETTC-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CC(C)C(O)(O)O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CC(C)C(O)(O)O JKVUNJFYNJETTC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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Abstract
特别适用于制备双极板的模塑组合物,包含(a)环氧树脂,(b)环氧树脂的固化剂,(c)含有羧酸基的微凝胶和含氮碱的反应产物,(d)电子导电填料混合物,以填料总量计该混合物含有至少75重量%的石墨。
Description
本发明涉及包含电子导电填料混合物的环氧树脂组合物和该组合物用于制备双极板的应用。
具有高导热性和电子导电性的模塑组合物在电气工业中的特殊应用日益重要,例如用于制备燃料电池的双极板。
WO99/19389描述了包含10-30重量%的低粘度树脂和70-90重量%的电子导电填料的热固化组合物。该组合物具有良好的导热性和电子导电性,抗裂性强。但是,只能在溶剂存在和/或使用液态树脂-固化剂成分时制备这些模塑组合物。
WO 00/25372中建议使用乙烯基酯树脂,石墨粉,和,如果适当的话,增强纤维的混合物作为制备双极板的复合材料。如果要求,在这些体系中不使用溶剂;但是这些产品不是用于实际应用时贮存稳定性不够,就是用于大规模生产时固化时间太长。当燃料电池在热的、湿润的气候下操作时,酸不可避免地从酯官能团上脱落,对催化剂和隔膜造成另外的问题。
本发明的一个目的是提供具有高导热性和电子导电性的无溶剂,贮存稳定,快速制造成压片形式固化的环氧树脂体系,该体系能够通过有效的方法(挤出,压延)制造成压片形式,并且,如果适当,特别是可采用用于环氧模塑组合物的通常的方法(注射模塑法,传递模塑法,压缩模塑法)加工该体系获得双极板。
这里特别困难的是为了得到足够好的导电性,在双极板中导电填料的加入量不得不非常高。同时,肯定不允许模塑组合物流动性随着填料含量增加而下降从而限制加工性。这里,另一个必须考虑的因素是:在引入至最终的压塑模具中之前,热固性模塑组合物任何预受热(例如:挤出,预塑化,在注射模塑筒中的停留时间)都会使其流动性由于固化反应开始而额外下降。尽管这种下降可以通过总体降低固化速度而得到抑制,但也会导致在模具温度下固化速度下降。如果要在1分钟以下的固化时间内能够有效地大量生产双极板,就特别要求在模具温度下,模塑组合物具有高固化速度。
理论上,可以通过使用液态或粘度非常低的树脂成分或者固化剂成分来抑制流动性随着填料含量的增加而降低。但是,该优点将伴随着一系列相当多的缺点或新问题:
1.液态成分更难以操作,连同有问题的均化步骤(将固体不溶成分均一地引入液体内,可能出现的沉降问题)将会导致从设备和时间的角度而言明显地总体上需要更多资源的生产方法。相反,只有固体的混合物可以用市售的高速搅拌器在几秒钟内搅拌均匀。那么,直接挤出机加工法就成为了可能。实际上,既然固体成分也可以直接计量引入挤出机并在其中混合,在理想状态下可以完全省略预混合步骤。
2.经验表明,随着液态基质成分含量的增加,当使用常规的压缩方法和参数时,例如在DIN7708中描述的(“Rieselfhigeduroplastische Formmassen-Herstellung von Probekrpern undBestimmung der Eigenschaften”[自由流动热固性模塑组合物-试验样品的制备和性质的测定]),或在ASTM D3123-72中(“低压热固化模塑混合物的螺旋流动”)中描述的,在适当的压力(>69巴)和压缩温度(150-190℃)下,预期从基质中会有或多或少的渗出。这里,基质通过模具的分离面从模具本身和周围的填料中排出,在分离面,这种排出形成了不希望的溢料,与之相关的缺点是已知的(增加了粘结倾向,需要机械后处理,材料损失)。同时,这种基质材料的损失导致了机械性能的降低,在极端情况下使得模塑物无法从模具中取出。另外,在模塑物表面的低填料含量的基质层会增加两双极板之间的接触电阻。另一方面,较低的压力导致压缩不充分,致使空气夹裹、增加收缩并在模塑过程中产生填充问题。
3.当基质含有液体,通常预期潜伏性较低,贮存稳定性较差。
现在已经发现,也可以不使用液态基质成分也就没有与之相连的缺点,通过同时使用特殊的微凝胶-胺催化剂和特定等级的石墨,而获得所需要的性能特性。
因此,本发明提供了一种组合物,其包含
(a)环氧树脂,
(b)环氧树脂的固化剂,
(c)含有羧酸基的微凝胶和含氮碱的反应产物,
(d)电子导电填料混合物,以填料总量计该混合物含有至少75重量%的石墨。
用于制备本发明的组合物的合适的成分(a)是环氧树脂技术中常用的环氧树脂。环氧树脂的例子有:
I)聚缩水甘油酯和聚(β-甲基缩水甘油基)酯,可通过在分子中包含至少2个羧基的化合物和表氯醇或β-甲基表氯醇反应获得。反应在碱存在下有效发生。
所使用的在分子中包含至少2个羧基的化合物可以是脂肪族的多元酸。此类多元酸的例子有草酸,琥珀酸,戊二酸,己二酸,庚二酸,辛二酸,壬二酸和二聚或三聚的亚油酸。
但是,也有可能使用脂环族多元酸,例如四氢邻苯二甲酸,4-甲基四氢邻苯二甲酸,六氢邻苯二甲酸,或4-甲基六氢邻苯二甲酸。
也可使用芳族多元酸,例如邻苯二甲酸,间苯二甲酸或对苯二甲酸。
II)聚缩水甘油醚或聚(β-甲基缩水甘油基)醚,可通过含有至少2个自由醇羟基和/或酚羟基的化合物和表氯醇或β-甲基表氯醇在碱性条件下反应或在酸催化剂存在下反应,然后用碱处理而获得。
这些缩水甘油醚衍生自例如非环形醇,例如,衍生于乙二醇,二甘醇,或更高级的聚氧乙二醇,丙-1,2-二醇或聚氧丙二醇,或丙-1,3-二醇,丁-1,4-二醇,聚氧四亚甲基二醇,戊-1,5-二醇,己-1,6-二醇,己-2,4,6-三醇,丙三醇,1,1,1-三羟甲基丙烷,季戊四醇或山梨醇,或者衍生于聚表氯醇。
其它这种类型的缩水甘油醚衍生于脂环族醇,例如1,4-环己烷二甲醇,双-(4-羟基环己基)甲烷,或2,2-双-(4-羟基环己基)-丙烷,或衍生自含有芳族基团和/或其它官能团的醇,例如N,N-双-(2-羟基乙基)-苯胺或p,p′-双-(2-羟基乙基氨基)-二苯基甲烷。
该缩水甘油醚也可基于单核的酚,例如间苯二酚或氢醌,或者基于多核的酚,例如双-(4-羟基苯基)-甲烷,4,4′-二羟基联苯,双-(4-羟基苯基)-砜,1,1,2,2-四-(4-羟基苯基)-乙烷,2,2-双-(4-羟基苯基)-丙烷或2,2-双-(3,5-二溴-4-羟基苯基)-丙烷。
其它适于制备缩水甘油醚的羟基化合物是线型酚醛清漆,其可以通过醛例如甲醛、乙醛、氯醛或糠醛与未取代或由氯原子或C1-C9烷基取代的酚类或双酚如苯酚,4-氯代苯酚,2-甲基苯酚或4-叔丁基苯酚缩合反应得到。
III)聚-(N-缩水甘油基)化合物,可以通过使表氯醇与含有至少两个胺氢原子的胺的反应产物脱去氯化氢得到。这里的胺例如苯胺、正丁基胺、双-(4-氨基苯基)甲烷、间-二甲苯二胺或双-(4-甲基氨基苯基)甲烷。
聚-(N-缩水甘油基)化合物还包含三缩水甘油基异氰脲酸酯、环亚烷基脲的N,N′-二缩水甘油基衍生物,环亚烷基脲如亚乙基脲或1,3-亚丙基脲,和乙内酰脲如5,5-二甲基乙内酰脲的二缩水甘油基衍生物。
IV)聚(S-缩水甘油基)化合物,例如由二硫醇如乙-1,2-二硫醇或双-(4-巯基甲基苯基)醚衍生的二-S-缩水甘油基衍生物。
V)脂环族环氧树脂,例如双-(2,3-环氧环戊基)-醚、2,3-环氧环戊基缩水甘油醚、1,2-双-(2,3-环氧环戊基氧)-乙烷或3,4-环氧环己基甲基-3′,4′-环氧环己烷羧酸酯。
也可以使用1,2-环氧基团连接在不同的杂原子或官能团上的环氧树脂;这些化合物例如4-氨基苯酚的N,N,O-三缩水甘油基衍生物、水杨酸的缩水甘油醚缩水甘油酯、N-缩水甘油基-N′-(2-缩水甘油基氧丙基)-5,5-二甲基乙内酰脲和2-缩水甘油基氧-1,3-双-(5,5-二甲基-1-缩水甘油基乙内酰脲-3-基)-丙烷。
为了制备本发明的环氧树脂组合物,优选使用固体聚缩水甘油醚或固体聚缩水甘油酯,特别是固体二缩水甘油双酚醚或脂环族或芳族二羧酸的固体二缩水甘油酯,或脂环族环氧树脂、也有可能使用环氧树脂的混合物。
优选使用固体醚基的环氧树脂。
可以使用化合物的熔点从高于室温到大约250℃的固体聚缩水甘油醚。固体化合物的熔点优选50-150℃。这些固体化合物是已知的,部分可以从市场上买到。作为固体聚缩水甘油醚也可以使用通过液体聚缩水甘油醚预扩链而得到的高级产物。
特别优选的成分(a)是环氧苯酚型酚醛清漆和环氧甲酚型酚醛清漆。
基本上环氧树脂技术领域的技术人员已知的任何固化剂可以作为成分(b)。
优选的固化剂是苯酚型酚醛清漆和甲酚型酚醛清漆。
从美国专利US5994475可知,含有羧酸基团的微凝胶与合N碱的反应产物(微凝胶-胺盐)可以作为成分(c)。
成分(C)中的微凝胶优选是至少一种不饱和羧酸特别是丙烯酸或甲基丙烯酸与至少一种多官能交联剂的共聚物。
优选用脂肪族、脂环族或芳香族多元醇的多官能丙烯酸酯或甲基丙烯酸酯,丙烯酸或甲基丙烯酸与多缩水甘油基化合物的加成产物,丙烯酸或甲基丙烯酸与丙烯酸或甲基丙烯酸缩水甘油酯的加成产物,链烯基丙烯酸酯或链烯基甲基丙烯酸酯,二链烯基环己烷或二链烯基苯作为制备组分(c)中微凝胶的多官能交联剂。
多官能交联剂特别优选是二丙烯酸乙二醇酯,二甲基丙烯酸乙二醇酯,二丙烯酸丙二醇酯,二甲基丙烯酸丙二醇酯,二丙烯酸1,4-丁二醇酯,二甲基丙烯酸1,4-丁二醇酯,二丙烯酸聚乙二醇酯,二甲基丙烯酸聚乙二醇酯,二丙烯酸聚丙二醇酯,二甲基丙烯酸聚丙二醇酯,1,1,1-三羟甲基丙烷三丙烯酸酯,1,1,1-三羟甲基丙烷三甲基丙烯酸酯,双酚A二缩水甘油醚二丙烯酸酯,双酚A二缩水甘油醚二甲基丙烯酸酯,丙烯酸烯丙基酯,甲基丙烯酸烯丙基酯,二乙烯基环己烷,二乙烯基苯。
优选胺,多胺或特别是咪唑作为制备成分(c)中的含氮碱。
特别优选的含氮碱是2-苯基咪唑,2-异丙基咪唑,2-十二烷基咪唑,2-十七烷基咪唑,2-乙基咪唑,和2-乙基-4-甲基咪唑。
本发明组合物的电子导电填料混合物(d)可以由纯石墨或与其它矿物或金属填料或碳黑的混合物组成,只要石墨在整个填料混合物(d)中的比例是至少75重量%,优选至少85重量%,特别优选至少95重量%。
填料的粒径也很重要。
所用石墨粉的平均粒径为0.1-500μm,更优选1-300μm,特别优选10-250μm,特别优选50-100μm。石墨具有层结构,电子沿着这些层流动。制备模塑极板时,随着粒度的增加这些层在板面上变得取向,所以板平面内的电子导电性要比横过板平面的导电性高。
由于具有低取向,优选使用合成石墨。与天然石墨不一样,合成石墨被二价或三价阳离子污染的程度低,这些阳离子能被包埋进燃料电池的隔膜内,从而降低了性能。
本发明的组合物中成分(a),(b),(c)和(d)的质量比例可以在宽范围内变化。
环氧树脂(a)与固化剂(b)的质量比例在本领域技术人员已知的常规范围内。优选以成分(a)的为100重量%计算,组合物中包含20-75重量%的成分(b)。
以成分(a)的为100重量%计算,成分(c)的用量为0.1-25重量%,优选1-20重量%。
以成分(a)+(b)+(c)+(d)的全部组合物为基础,填料混合物d)的用量为50-90重量%,优选70-85重量%。
本发明的组合物也可含有其它常规添加剂,例如:抗氧化剂,光稳定剂,增塑剂,染料,颜料,触变剂,增韧剂,消泡剂,抗静电剂,润滑剂和脱模剂。这些助剂的含量包含在填料成分(d)中。
令人惊奇地是通过加入有机硅烷,可使固化的环氧树脂电子导电性显著增加。合适的有机硅烷的例子有:辛基三乙氧基硅烷,甲基三乙氧基硅烷,乙烯基三乙氧基硅烷,甲基三甲氧基硅烷,乙烯基三甲氧基硅烷,γ-氨丙基三甲氧基硅烷和γ-缩水甘油基氧丙基三甲氧基硅烷。
硅烷的添加量优选占全部组合物的0.05-1重量%,特别是0.1-0.5重量%。
固化树脂的机械性能随着制剂中石墨比例的增加而变差。从文献中已知可用纤维填料增加机械性能。但是例如WO00/25372所描述的,加入纤维填料后就不得不接受表面质量损失,模塑组合物加工性变差,纤维取向的风险,特别是在大表面积应用中,例如双极板。已经发现,环氧树脂基质的性能特性足够好,即使成分(a)+(b)+(c)的比例仅仅是15-30重量%,所获得的强度使得在脱模和组装燃料电池的过程中,极板也可可靠操作。不使用纤维填料,可使模塑物具有非常精细的结构和特别好的表面质量。
可以环氧树脂技术领域公知的方式将本发明的环氧树脂组合物固化为模塑物、涂层等,比如参见H.Lee和K.Neville的“Handbookof Epoxy Resins”,1976中所述。
本发明也提供通过固化本发明的组合物而制备的电子导电材料。
本发明的组合物适用于代替电气应用中的金属,特别适合制备燃料电池的双极板。
制备PEM燃料电池需要大量的双极板。为了具有在低成本下制造如此多的双极板的能力,制备方法必须能在非常短的循环时间内和高自动化水平下运行。为达到这种性能特性,需要模塑组合物的潜伏性高。
以下的实施例中使用下列成分:
环氧树脂1:环氧甲酚型酚醛清漆,环氧含量4.35val/kg
环氧树脂2:双酚A二缩水甘油醚,环氧含量2.2val/kg
固化剂1:甲酚型酚醛清漆,羟基含量8.5val/kg
催化剂1:微凝胶-胺盐,按专利US5994475实施例11.5的方法,从甲基丙烯酸甲酯,甲基丙烯酸,二甲基丙烯酸乙二醇酯,三羟甲基丙烷三甲基丙烯酸酯和2,4-乙基甲基咪唑制备。
EMI:2,4-乙基甲基咪唑
平均粒径20μm的石墨粉
本发明的组合物(见实施例1)在60-100℃下具有高潜伏性。这点是很重要的。因为在加工过程中,组合物必须被加热到这样的温度以预塑化。同时,因为组合物本身填料水平高而使得其粘度高,必须避免粘度的任何进一步增加,以确保在模具填充过程中组合物具有足够的流动性。为了模拟模塑组合物在加工过程中的这种特性,将得自实施例1的模塑组合物压片在压延机中,在两个不同温度设定下调节了3和6分钟,比较了螺旋流动路径的变化。表1清楚地表明含有EMI的产品的流动性即使在开始时流动性也相对差,当其从初始下降了30-40%时,使用微凝胶催化剂的产品的流动性仅仅下降了13-15%。在实践中,这意味着对按常规方法加速的模塑组合物而言,在生产中即使小间歇也会对双极板的质量有显著影响。流动性差的模塑组合物的许多缺点之一是它们不能充分压制,这将导致极极气密性降低,而气密性是PEM燃料电池可靠运行的首要要求。
实施例1:流动性和潜伏性
将表1给出的成分在球磨中混合,在压延机中在90-110℃下均化。然后按照ASTMD3123测定获得的压片的流动性。
表1:
成分 | A(本发明) | B(对比例) |
a)环氧树脂1a)环氧树脂2b)固化剂1c)催化剂1EMI(对比例)d)石墨粉(20μm)d)硬脂酸钙d)Hoechst OP 125U蜡 | 13.378.699.641.8065.00.501.00 | 13.378.699.640.3866.420.501.00 |
总计 | 100 | 100 |
使用压延机混合,170℃螺旋流动[英寸/厘米]混合3分钟(后/前辊)温度为90/100℃100/110℃混合6分钟(后/前辊)温度为90/100℃100/110℃ | 20.0/50.818.0/45.717.25/43.815.5/39.4 | 13.5/34.39.75/24.88/20.36.75/17.1 |
实施例2:体积电阻率
当比较组合物C和D时,有机硅烷对固化混合物的体积电阻率的影响是明显的。表2中,成分的质量数据是重量份。
表2:
成分 | C | D |
a)环氧树脂1a)环氧树脂2b)固化剂1c)催化剂1d)Sikron B 300粉状石英d)PPG EC10d)石墨粉(20μm)d)γ-缩水甘油基氧丙基三甲氧基硅烷d)硬脂酸钙 | 11.477.468.271.809.505.0055.000.50 | 11.477.468.271.809.305.0055.000.200.50 |
d)Hoechst OP 125U蜡 | 1.00 | 1.00 |
体积电阻率[ohm cm] | 0.305 | 0.218 |
本领域目前的情况要求双极板的体积电阻率<0.1ohm cm,以避免对燃料电池性能有任何负面影响。典型地使用直径3.5cm,厚度至少1.5cm的圆形试样(压制物)进行测量。因为该方法在很大程度上取决于电极和压制物之间的接触面积,施加于试样上的压力为1-5N/mm2。数值上的变化可以作为评定压制物表面质量的判据。如果目的是为了消除不均匀性对电导率的影响,可将软石墨垫放于电极和压制物之间。图1表示用于测定体积电阻率的一种合适的测试组件的图。图中的参考数字表示1=固定器,2=加载单元,3=绝缘体,4=石墨垫,5=接点,6=试样,7=电压表,8=电流表和9=电源。这里使用的测量原理以一种4点式电导率测量系统电路图的形式表示在图2中。图2中的参考数字表示:1=电源,2=试样,3=电流表,4=电压表。
下表3表明需要使用高石墨含量以达到这些低电阻率。不幸的是体积电阻率的降低还伴随着流动性的降低,该效应在表3中也很明显。表3中成分的质量数据是重量份。
表3:
成分 | E | F | G | H |
环氧树脂1环氧树脂2固化剂1催化剂1石墨粉(20μm),合成的硬脂酸钙Hoechst OP 125U蜡 | 15.4810.0611.161.8060.000.501.00 | 13.378.699.641.8065.000.501.00 | 11.267.328.121.8070.000.501.00 | 9.155.956.601.8075.000.501.00 |
总计 | 100.00 | 100.00 | 100.00 | 100.00 |
体积电阻率[ohm cm] | 1.09 | 0.37 | 0.22 | 0.13 |
螺旋流动[英寸] | 29.5 | 17.5 | 11.0 | 5.0 |
石墨等级的选择
通过对成分(d)适宜的粒度分析可以使制剂的螺旋流动性和电导率最佳。这里应主要使用合成石墨,因为天然石墨包含1-3%的多价阳离子,这些阳离子可以被包埋进隔膜内而产生负面效应。下表4表示了上述制剂G(表3)的体积电导率是所使用的石墨等级的函数。括号内的数据是石墨的平均粒径。
表4:
实施例 | 石墨等级 | 体积电阻率[ohm cm] | 螺旋流动(170℃)[英寸/厘米] |
G | 合成(20μm) | 0.22 | 11.0/27.9 |
H | 合成(50μm) | 0.14 | 23.0/58.4 |
I | 合成(60μm) | 0.08 | 14.5/36.8 |
J | 合成(100μm) | 0.12 | 22.0/55.9 |
K | 合成(250μm) | 0.18 | 30.5/77.5 |
L | 合成(500μm) | 0.16 | 31.0/78.7 |
M | 天然薄片(50μm) | 0.17 | 21.0/53.3 |
N | 天然薄片(100μm) | 0.19 | 25.0/63.5 |
0 | 天然薄片(250μm) | 0.10 | 34.0/86.4 |
P | 天然薄片(300μm) | 0.16 | 31.0/78.7 |
这些制剂的流动性随着石墨粒径的增加而自然增加(见表4),但与此同时固化的模塑组合物表面质量也受到损害。模塑组合物产生溢料的倾向增加,因此后处理操作的需求增加。
根据表4,使用平均粒径大约60μm的合成级的石墨可产生最大的电导性。这里证明,以成分(a)+(b)+(c)+(d)的整个组合物为基础,73重量%的石墨比例可以在电导性和流动性之间获得最佳的平衡。将这种最佳制剂的流动性与同样制剂但使用EMI催化的变体的流动性相比较,也可以发现由于流动性不够(实施例S和T)使用EMI导致加工性不够。为达到此目的,制剂在混合压延机中,在辊温100/110℃下均化3和4分钟。
EMI催化的实施例I的螺旋流动路径经过短短4分钟后减少了一半,然而发现微凝胶变体(实施例Q和R)只有从10到9英寸的小变化(从25.4到22.9cm)。见下表5。
压延机中加工参数的选择要使模塑组合物的流动性质(螺旋路径)与挤出方法的流动性质相似。如果混合过程之后螺旋流动路径≤5英寸(12.7cm),就不能获得令人满意的加工。依赖于组合物的潜伏特性,如果组合物在实际使用过程之前受到其它热影响(例如压缩法预塑化),则该值增大。
表5:
成分 | Q(3分钟) | R(4分钟) | S(3分钟) | T(4分钟) |
a)环氧树脂1a)环氧树脂2b)固化剂1c)催化剂1EMI(对比例)d)石墨粉(60μm),合成的d)硬脂酸钙d)Hoechst OP 125U蜡 | 9.996.507.211.8073.000.501.00 | 9.996.507.211.8073.000.501.00 | 10.146.597.320.3974.060.501.00 | 10.146.597.320.3974.060.501.00 |
总计 | 100 | 100 | 100 | 100 |
体积电阻率[ohm cm] | 0.05 | 0.05 | 0.05 | 0.05 |
螺旋流动路径[英寸/厘米] | 10/25.4 | 9/22.9 | 4/10.1 | 2/2.6 |
制剂Q的性质如下表6所示:
表6:
压片的性质 | |
160℃塑度计B值[Nm] | 1.2 |
160℃塑度计AD值[秒] | 71 |
120℃塑度计B值[Nm] | 4.6 |
120℃塑度计AD值[秒] | 285 |
170℃螺旋流动11值[英寸] | 10 |
170℃邵氏D-脱模性 | 65;好 |
一般性质 | |
密度[g/cm3] | 1.78 |
1mm板脱模性 | 好 |
1mm板稳定性 | 好 |
170℃下收缩(%) | 0.16×0.15 |
机械性能 | |
弯曲强度[MPa] | 51 |
弹性模量[GPa] | 16 |
断裂伸长率[%] | 0.35 |
抗冲击强度[KJ/m2] | 1.5 |
热性能 | |
玻璃化转变温度[℃] | 164 |
导热系数[W/m·K] | >15 |
体积电阻率 | |
没有表层的板[ohm·cm] | 0.01-0.03 |
具有初始表面的板[ohm·cm] | 0.05 |
Claims (15)
1.组合物,包含
(a)环氧树脂,
(b)环氧树脂的固化剂,
(c)含有羧酸基的微凝胶和含氮碱的反应产物,
(d)电子导电填料混合物,其含有以填料总量计至少75重量%的石墨。
2.根据权利要求1的组合物,包含环氧苯酚型酚醛清漆或环氧甲酚型酚醛清漆作为成分(a)。
3.根据权利要求1或2的组合物,其中成分(c)中的微凝胶是至少一种不饱和羧酸与至少一种多官能交联剂的共聚物。
4.根据权利要求3的组合物,其中不饱和羧酸是丙烯酸或甲基丙烯酸。
5.根据权利要求3的组合物,其中多官能交联剂是脂肪族、脂环族或芳香族多元醇的多官能丙烯酸酯或甲基丙烯酸酯,丙烯酸或甲基丙烯酸与多缩水甘油基化合物的加成产物,丙烯酸或甲基丙烯酸与丙烯酸或甲基丙烯酸缩水甘油酯的加成产物,链烯基丙烯酸酯或链烯基甲基丙烯酸酯,二链烯基环己烷或二链烯基苯。
6.根据权利要求3的组合物,其中多官能交联剂选自二丙烯酸乙二醇酯,二甲基丙烯酸乙二醇酯,二丙烯酸丙二醇酯,二甲基丙烯酸丙二醇酯,二丙烯酸1,4-丁二醇酯,二甲基丙烯酸1,4-丁二醇酯,二丙烯酸聚乙二醇酯,二甲基丙烯酸聚乙二醇酯,二丙烯酸聚丙二醇酯,二甲基丙烯酸聚丙二醇酯,1,1,1-三羟甲基丙烷三丙烯酸酯,1,1,1-三羟甲基丙烷三甲基丙烯酸酯,双酚A二缩水甘油醚二丙烯酸酯,双酚A二缩水甘油醚二甲基丙烯酸酯,丙烯酸烯丙基酯,甲基丙烯酸烯丙基酯,二乙烯基环己烷和二乙烯基苯。
7.根据权利要求1或2的组合物,其中成分(c)中的含氮碱是胺,多胺或咪唑。
8.根据权利要求7的组合物,其中含氮碱是2-苯基咪唑,2-异丙基咪唑,2-十二烷基咪唑,2-十七烷基咪唑,2-乙基咪唑,或2-乙基-4-甲基咪唑。
9.根据权利要求1的组合物,其中填料混合物(d)包含平均粒径为0.1-500μm,优选1-300μm,更优选10-250μm,特别优选50-100μm的石墨粉。
10.根据权利要求1的组合物,其中填料混合物(d)包含合成石墨形式的石墨粉。
11.根据权利要求1的组合物,以成分(a)为100重量份计算,组合物包含0.1-25重量份的成分(c)。
12.根据权利要求1的组合物,以成分(a)+(b)+(c)+(d)的全部组合物为基准,包含50-90重量%,优选70-85重量%的成分(d)。
13.根据权利要求1的组合物,还包含有机硅烷。
14.通过固化权利要求1的组合物得到的电子导电材料。
15.根据权利要求1的组合物用于制备双极板的用途。
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EP (1) | EP1387860B1 (zh) |
JP (2) | JP4098094B2 (zh) |
KR (1) | KR100881311B1 (zh) |
CN (1) | CN1219803C (zh) |
AT (1) | ATE299905T1 (zh) |
CA (1) | CA2445721C (zh) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100454624C (zh) * | 2005-08-31 | 2009-01-21 | 三星Sdi株式会社 | 燃料电池系统及其所使用的单元电池和双极板 |
CN101308923B (zh) * | 2007-05-18 | 2010-05-19 | 大连融科储能技术发展有限公司 | 一种液流储能电池用碳塑导电复合双极板及其制备 |
CN102074714A (zh) * | 2010-12-17 | 2011-05-25 | 湖南大学 | 一种以过渡金属—石墨层间复合物为填料制备燃料电池双极板的方法 |
CN104231548A (zh) * | 2014-03-04 | 2014-12-24 | 上海大学 | 台面板用复合型环氧树脂材料 |
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DE102004062551A1 (de) * | 2004-12-24 | 2006-07-06 | Rhein Chemie Rheinau Gmbh | Mikrogel-enthaltende duroplastische Zusammensetzung |
US20100330462A1 (en) * | 2009-06-25 | 2010-12-30 | Gas Technology Institute | Corrosion resistant molded graphite plates for highly corrosive electrochemical devices |
JP5700238B2 (ja) * | 2009-09-02 | 2015-04-15 | 三菱レイヨン株式会社 | エポキシ樹脂用硬化剤、エポキシ樹脂組成物及びエポキシ樹脂硬化物 |
JP2011134978A (ja) * | 2009-12-25 | 2011-07-07 | Fuji Electric Co Ltd | 流体冷却式ヒートシンク |
SG188261A1 (en) | 2010-09-02 | 2013-04-30 | Sumitomo Bakelite Co | Fixing resin composition for use in rotor |
JP5730375B2 (ja) * | 2013-10-31 | 2015-06-10 | キヤノン株式会社 | 画像処理装置及びその制御方法、並びに、プログラム |
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US4217401A (en) * | 1978-07-10 | 1980-08-12 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Bipolar separator for electrochemical cells and method of preparation thereof |
JPS63142085A (ja) * | 1986-12-05 | 1988-06-14 | Showa Denko Kk | 導電性シ−ト状接着剤の製造法 |
JPH06114387A (ja) * | 1992-10-08 | 1994-04-26 | Nippon Shokubai Co Ltd | 水処理方法 |
EP0816393B1 (de) * | 1996-07-02 | 2003-11-19 | Vantico AG | Härter für Epoxidharze |
WO1999019389A1 (en) * | 1997-10-14 | 1999-04-22 | Cytec Technology Corp. | Conductive thermoset molding composition and method for producing same |
US6248467B1 (en) | 1998-10-23 | 2001-06-19 | The Regents Of The University Of California | Composite bipolar plate for electrochemical cells |
DE60016295T2 (de) * | 1999-02-16 | 2005-05-04 | Nichias Corp. | Harzzusammensetzung |
US6562884B1 (en) * | 1999-03-17 | 2003-05-13 | Vantico, Inc. | Epoxy resin compositions having a long shelf life |
JP4780257B2 (ja) | 2000-02-03 | 2011-09-28 | 日清紡ホールディングス株式会社 | 燃料電池セパレータ及びその製造方法 |
DE10196589T1 (de) * | 2000-08-14 | 2003-07-10 | World Properties Inc | Wärmehärtbare Zusammensetzung für Bauteile einer elektrochemischen Zelle und Verfahren zu deren Herstellung |
EP1189297A3 (en) * | 2000-09-13 | 2004-04-07 | Mitsui Takeda Chemicals, Inc. | Separator for solid polymer type fuel cell and process for producing the same |
JP4362359B2 (ja) * | 2003-12-26 | 2009-11-11 | 本田技研工業株式会社 | 燃料電池及び燃料電池スタック |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100454624C (zh) * | 2005-08-31 | 2009-01-21 | 三星Sdi株式会社 | 燃料电池系统及其所使用的单元电池和双极板 |
CN101308923B (zh) * | 2007-05-18 | 2010-05-19 | 大连融科储能技术发展有限公司 | 一种液流储能电池用碳塑导电复合双极板及其制备 |
CN102074714A (zh) * | 2010-12-17 | 2011-05-25 | 湖南大学 | 一种以过渡金属—石墨层间复合物为填料制备燃料电池双极板的方法 |
CN104231548A (zh) * | 2014-03-04 | 2014-12-24 | 上海大学 | 台面板用复合型环氧树脂材料 |
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JP2004526850A (ja) | 2004-09-02 |
JP2008179786A (ja) | 2008-08-07 |
US20070185244A1 (en) | 2007-08-09 |
US20040147643A1 (en) | 2004-07-29 |
JP5026244B2 (ja) | 2012-09-12 |
CN1219803C (zh) | 2005-09-21 |
WO2002092659A1 (en) | 2002-11-21 |
US7695806B2 (en) | 2010-04-13 |
CA2445721C (en) | 2010-07-13 |
EP1387860A1 (en) | 2004-02-11 |
JP4098094B2 (ja) | 2008-06-11 |
DE60205105D1 (de) | 2005-08-25 |
EP1387860B1 (en) | 2005-07-20 |
CA2445721A1 (en) | 2002-11-21 |
ES2245740T3 (es) | 2006-01-16 |
DE60205105T2 (de) | 2006-04-20 |
KR100881311B1 (ko) | 2009-02-03 |
ATE299905T1 (de) | 2005-08-15 |
KR20030090796A (ko) | 2003-11-28 |
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