JP4656250B2 - 耐熱性膨張黒鉛シート - Google Patents
耐熱性膨張黒鉛シート Download PDFInfo
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- JP4656250B2 JP4656250B2 JP2009205957A JP2009205957A JP4656250B2 JP 4656250 B2 JP4656250 B2 JP 4656250B2 JP 2009205957 A JP2009205957 A JP 2009205957A JP 2009205957 A JP2009205957 A JP 2009205957A JP 4656250 B2 JP4656250 B2 JP 4656250B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 195
- 229910002804 graphite Inorganic materials 0.000 title claims description 185
- 239000010439 graphite Substances 0.000 title claims description 185
- 125000004432 carbon atom Chemical group C* 0.000 claims description 78
- 125000003118 aryl group Chemical group 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 21
- -1 phosphate ester Chemical class 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 17
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 7
- 150000008301 phosphite esters Chemical class 0.000 claims description 5
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 40
- 239000002245 particle Substances 0.000 description 39
- 239000000203 mixture Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 239000007770 graphite material Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- WTQARTIGFMEZNX-UHFFFAOYSA-N dimethoxyphosphane Chemical compound COPOC WTQARTIGFMEZNX-UHFFFAOYSA-N 0.000 description 8
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 7
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- GVFPRYAPMFINSY-UHFFFAOYSA-N 1-dimethylphosphoryloxyethane Chemical compound CCOP(C)(C)=O GVFPRYAPMFINSY-UHFFFAOYSA-N 0.000 description 1
- TYFJTEPDESMEHE-UHFFFAOYSA-N 6,8-dihydroxy-3-[2-(4-methoxyphenyl)ethyl]-3,4-dihydroisochromen-1-one Chemical compound C1=CC(OC)=CC=C1CCC1OC(=O)C2=C(O)C=C(O)C=C2C1 TYFJTEPDESMEHE-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- PHIBEYMUALDAQI-UHFFFAOYSA-N benzylphosphinic acid Chemical compound OP(=O)CC1=CC=CC=C1 PHIBEYMUALDAQI-UHFFFAOYSA-N 0.000 description 1
- OEGCNNRUVSIMHC-UHFFFAOYSA-N bis(phenylmethoxy)phosphane Chemical compound C=1C=CC=CC=1COPOCC1=CC=CC=C1 OEGCNNRUVSIMHC-UHFFFAOYSA-N 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HDFFVHSMHLDSLO-UHFFFAOYSA-M dibenzyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)([O-])OCC1=CC=CC=C1 HDFFVHSMHLDSLO-UHFFFAOYSA-M 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- RVDJLKVICMLVJQ-UHFFFAOYSA-N diethoxy(phenyl)phosphane Chemical compound CCOP(OCC)C1=CC=CC=C1 RVDJLKVICMLVJQ-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- KDBYJAXRGTUGSC-UHFFFAOYSA-N diphenoxyphosphane Chemical compound C=1C=CC=CC=1OPOC1=CC=CC=C1 KDBYJAXRGTUGSC-UHFFFAOYSA-N 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- AGWPTXYSXUNKLV-UHFFFAOYSA-N ethoxy-methyl-oxophosphanium Chemical compound CCO[P+](C)=O AGWPTXYSXUNKLV-UHFFFAOYSA-N 0.000 description 1
- YJSXLGKPMXKZJR-UHFFFAOYSA-N ethoxy-oxo-phenylphosphanium Chemical compound CCO[P+](=O)C1=CC=CC=C1 YJSXLGKPMXKZJR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DWHMMGGJCLDORC-UHFFFAOYSA-N methoxy(methyl)phosphinic acid Chemical compound COP(C)(O)=O DWHMMGGJCLDORC-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- VOWPVJACXJNHBC-UHFFFAOYSA-N methyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC)OC1=CC=CC=C1 VOWPVJACXJNHBC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RMJCJLHZCBFPDN-UHFFFAOYSA-N methyl(phenyl)phosphinic acid Chemical compound CP(O)(=O)C1=CC=CC=C1 RMJCJLHZCBFPDN-UHFFFAOYSA-N 0.000 description 1
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- MSVORCUEJCHPKS-UHFFFAOYSA-N phenoxy(phenyl)phosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)OC1=CC=CC=C1 MSVORCUEJCHPKS-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- XKCQASMZNPBLKI-UHFFFAOYSA-N phosphorosooxymethane Chemical compound COP=O XKCQASMZNPBLKI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/536—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite based on expanded graphite or complexed graphite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
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- C09K21/12—Organic materials containing phosphorus
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
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Description
濃度98%の濃硫酸300重量部を攪拌しながら、酸化剤として過酸化水素の60%水溶液5重量部を加え、これを反応液とする。この反応液を冷却して10℃の温度に保持し、粒度30〜80メッシュの鱗片状天然黒鉛粉末を添加し、30分間反応を行う。反応後、吸引濾過して酸処理黒鉛を分離し、該酸処理黒鉛を水で10分間攪拌して吸引濾過するという洗浄作業を2回繰り返し、酸処理黒鉛から硫酸分を十分除去する。ついで、硫酸分を十分除去した酸処理黒鉛を110℃の温度に保持した乾燥炉で3時間乾燥し、これを酸処理黒鉛原料とする。
前記製造方法Iと同様にして酸処理黒鉛原料を作製する。この酸処理黒鉛原料を950〜1200℃の温度で1〜10秒間加熱(膨張)処理して、分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張黒鉛粒子(膨張倍率200〜300倍)を形成する。このようにして得た膨張黒鉛粒子に有機リン化合物の粉末又は溶液を所定量の割合で配合し、均一に攪拌して混合物を得る。この混合物を双ローラー装置に供給してロール成形し、所望の厚さの耐熱性膨張黒鉛シートを作製する。
濃度98%の濃硫酸300重量部を撹拌しながら、酸化剤として過酸化水素の60%水溶液5重量部を加え、これを反応液とした。この反応液を冷却して10℃の温度に保持し、粒度30〜80メッシュの鱗片状天然黒鉛粉末100重量部を添加し、30分間反応を行った。反応後、吸引濾過して酸処理黒鉛を分離し、該酸処理黒鉛を300重量部の水で10分間撹拌して吸引濾過するという洗浄作業を2回繰り返し、酸処理黒鉛から硫酸分を充分除去した。ついで、硫酸分を充分除去した酸処理黒鉛を110℃の温度に保持した乾燥炉で3時間乾燥し、これを酸処理黒鉛原料とした。
前記実施例と同様にして、酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に、有機リン化合物としてフェニルホスホン酸ジエチルの粉末を(9)1.0重量部、(10)2.0重量部、(11)4.2重量部、(12)6.4重量部それぞれ配合し、均一に攪拌混合して4種類の混合物を得た。これらの混合物をそれぞれ、1000℃の温度で5秒間加熱処理して分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張倍率240倍の膨張黒鉛粒子を得た。この膨張処理工程において、フェニルホスホン酸ジエチルは膨張黒鉛粒子に分散含有されている。
前記実施例と同様にして、酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に、有機リン化合物としてジフェニルホスフィン酸の粉末を(13)1.0重量部、(14)2.0重量部、(15)4.2重量部、(16)6.4重量部それぞれ配合し、均一に攪拌混合して4種類の混合物を得た。これらの混合物を、1000℃の温度で5秒間加熱処理して分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張倍率240倍の膨張黒鉛粒子を得た。この膨張処理工程において、ジフェニルホスフィン酸は膨張黒鉛粒子に分散含有されている。
前記実施例と同様にして、酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に、有機リン化合物としてフェニルホスフィン酸の粉末を(17)1.0重量部、(18)2.0重量部、(19)4.2重量部、(20)6.4重量部それぞれ配合し、均一に攪拌混合して4種類の混合物を得た。これらの混合物を、1000℃の温度で5秒間加熱処理して分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張倍率240倍の膨張黒鉛粒子を得た。この膨張処理工程において、フェニルホスフィン酸は膨張黒鉛粒子に分散含有されている。
前記実施例と同様にして、酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に、有機リン化合物としてリン酸エステル、具体的にはリン酸ジフェニルの粉末を(21)1.0重量部、(22)2.0重量部、(23)4.2重量部、(24)6.4重量部それぞれ配合し、均一に攪拌混合して4種類の混合物を得た。これらの混合物を、1000℃の温度で5秒間加熱処理して分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張倍率240倍の膨張黒鉛粒子を得た。この膨張処理工程において、リン酸ジフェニルは膨張黒鉛粒子に分散含有されている。
前記実施例と同様にして、酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に、有機リン化合物として亜リン酸エステル、具体的には亜リン酸トリフェニルの溶液を(25)1.0重量部、(26)2.0重量部、(27)4.2重量部、(28)6.4重量部それぞれ噴霧状に配合し、均一に攪拌混合して4種類の混合物を得た。これらの混合物を、1000℃の温度で5秒間加熱処理して分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張倍率240倍の膨張黒鉛粒子を得た。この膨張処理工程において、亜リン酸トリフェニルは膨張黒鉛粒子に分散含有されている。
前記実施例と同様にして、酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に、有機リン化合物として次亜リン酸エステル、具体的にはジメチルホスホナイトの粉末を(29)1.0重量部、(30)2.0重量部、(31)4.2重量部、(32)6.4重量部それぞれ配合し、均一に攪拌混合して4種類の混合物を得た。これらの混合物を、1000℃の温度で5秒間加熱処理して分解ガスを発生せしめ、そのガス圧により黒鉛層間を拡張して膨張倍率240倍の膨張黒鉛粒子を得た。この膨張処理工程において、ジメチルホスホナイトは膨張黒鉛粒子に分散含有されている。
前記実施例と同様にして酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に濃度84%のオルトリン酸水溶液を(1)0.33重量部、(2)0.99重量部、(3)1.66重量部の割合で噴霧状に配合し、均一に撹拌して湿潤性を有する混合物を作製した。以下、前記実施例と同様の方法で、膨張倍率250倍の膨張黒鉛粒子を作製し、前記実施例と同様の方法で厚さ0.38mmの膨張黒鉛シートを作製した。この比較例で、酸処理黒鉛原料の配合したオルトリン酸は膨張処理工程において脱水反応を生じて五酸化リンを生成する。このようにして作製した膨張黒鉛シートは、(1)五酸化リン0.2重量%及び膨張黒鉛99.8重量%、(2)五酸化リン0.6重量%及び膨張黒鉛99.4重量%、(3)五酸化リン1.0重量%及び膨張黒鉛99.0重量%を含んでいる。
前記実施例と同様にして酸処理黒鉛原料を作製した。該酸処理黒鉛原料100重量部を撹拌しながら、該酸処理黒鉛原料に濃度50%の第一リン酸アルミニウム水溶液(4)8.4重量部、(5)17.4重量部、(6)38重量部をメタノール30重量部で希釈した溶液を噴霧状に配合し、均一に撹拌して湿潤性を有する混合物を作製した。以下、前記実施例と同様の方法で、膨張倍率250倍の膨張黒鉛粒子を作製し、前記実施例と同様の方法で厚さ0.38mmの膨張黒鉛シートを作製した。このようにして作製した膨張黒鉛シートは、(4)第一リン酸アルミニウム4.0重量%及び膨張黒鉛96.0重量%、(5)第一リン酸アルミニウム8.0重量%及び膨張黒鉛92.0重量%、(6)第一リン酸アルミニウム16.0重量%及び膨張黒鉛84.0重量%を含んでいる。
Claims (6)
- 有機リン化合物が0.1〜10重量%の割合で分散含有されている耐熱性膨張黒鉛シートであって、有機リン化合物が、有機ホスホン酸及びそのエステル、有機ホスフィン酸及びそのエステル、リン酸エステル、亜リン酸エステル並びに次亜リン酸エステルから選択される耐熱性膨張黒鉛シート。
- 亜リン酸エステルが下記一般式(4)で表される亜リン酸トリエステル並びに下記一般式(5)で表される亜リン酸ジエステル及び亜リン酸モノエステルから選択される請求項1に記載の耐熱性膨張黒鉛シート。
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EP1559680B1 (en) * | 2002-09-26 | 2012-01-25 | Oiles Corporation | Heat-resistant exfoliated graphite sheet |
WO2004038263A1 (ja) * | 2002-10-08 | 2004-05-06 | Oiles Corporation | 球帯状シール体 |
JP2006064296A (ja) * | 2004-08-27 | 2006-03-09 | Sgl Carbon Ag | 膨張黒鉛から成る熱伝導板とその製造方法 |
US8808850B2 (en) | 2011-10-25 | 2014-08-19 | Arclin | Water resistant intumescent fire retardant coating |
DE102015011952A1 (de) * | 2015-09-18 | 2017-03-23 | Sgl Carbon Se | Kathodenboden, Verfahren zur Herstellung eines Kathodenbodens und Verwendung desselben in einer Elektolysezelle zur Herstellung von Aluminium |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01252512A (ja) * | 1988-03-31 | 1989-10-09 | Union Kaabaito Services Kk | 改質黒鉛材 |
JPH10101316A (ja) * | 1996-09-30 | 1998-04-21 | Sekisui Chem Co Ltd | 可撓性グラファイト複合難燃組成物及び難燃シート |
JP4506465B2 (ja) * | 2002-09-26 | 2010-07-21 | オイレス工業株式会社 | 耐熱性膨張黒鉛シート |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3423496A (en) * | 1966-04-04 | 1969-01-21 | Dow Chemical Co | Process for preparing resilient graphite structures |
US3719608A (en) * | 1968-11-12 | 1973-03-06 | Dow Chemical Co | Oxidation resistant graphite compositions |
US4146401A (en) | 1975-08-02 | 1979-03-27 | Hitachi Chemical Company, Ltd. | Graphite material having compressibility and recovering property and method for manufacturing the same |
JPS55118987A (en) | 1979-03-06 | 1980-09-12 | Dainichi Nippon Cables Ltd | Foaming fireproof composition |
JPS5934021A (ja) | 1982-08-16 | 1984-02-24 | Oiles Ind Co Ltd | 耐熱性を有する摺動部材及びその製造方法 |
JPS6057062A (ja) | 1983-09-09 | 1985-04-02 | Oiles Ind Co Ltd | 耐熱性を有するしゆう動部材及びその製造方法 |
JP2635108B2 (ja) | 1988-07-01 | 1997-07-30 | 日本バルカー工業株式会社 | グランドパッキン組立体 |
US4951954A (en) | 1989-08-23 | 1990-08-28 | Acs Industries, Inc. | High temperature low friction seal |
DE4016710A1 (de) | 1990-05-24 | 1991-11-28 | Bayer Ag | Verfahren zur herstellung von formteilen |
DE4117077A1 (de) * | 1991-05-25 | 1992-11-26 | Bayer Ag | Verfahren zur herstellung von formkoerpern |
US5382387A (en) * | 1991-07-15 | 1995-01-17 | Bayer Aktiengesellschaft | Mouldings containing expandable graphite, their production and their use |
JP3139179B2 (ja) | 1992-10-12 | 2001-02-26 | オイレス工業株式会社 | 球帯状シール体 |
JP3261767B2 (ja) | 1992-10-12 | 2002-03-04 | オイレス工業株式会社 | 球帯状シール体ならびにその製造方法 |
JP3937473B2 (ja) | 1996-03-22 | 2007-06-27 | オイレス工業株式会社 | 摺動部材用組成物および該組成物からなる摺動部材ならびに球帯状シール体 |
US5997979A (en) | 1996-06-27 | 1999-12-07 | Oiles Corporation | Spherical annular seal member and method of manufacturing the same |
EP0824134A1 (en) * | 1996-08-13 | 1998-02-18 | Tosoh Corporation | Fire-retardant tablet, fire-retardant polymer composition and molded article employing the same |
JPH10110158A (ja) | 1996-10-07 | 1998-04-28 | Sekisui Chem Co Ltd | シール材 |
JP3812035B2 (ja) | 1997-02-10 | 2006-08-23 | オイレス工業株式会社 | 球帯状シール体ならびにその製造方法 |
US6228914B1 (en) | 1998-01-02 | 2001-05-08 | Graftech Inc. | Intumescent composition and method |
US6102995A (en) * | 1998-03-06 | 2000-08-15 | Georgia-Pacific Resins, Inc. | High performance intumescent system for imparting heat/flame resistance to thermally unstable substrates |
JP3430243B2 (ja) | 1999-07-14 | 2003-07-28 | 東洋炭素株式会社 | 耐熱性膨張黒鉛シート及びその製造方法 |
JP2001131426A (ja) | 1999-11-01 | 2001-05-15 | Toray Ind Inc | 導電性樹脂組成物およびその成形品 |
JP4420497B2 (ja) | 1999-11-29 | 2010-02-24 | 株式会社共和 | ダクトフランジ接合部用シール材 |
JP2001262146A (ja) | 2000-03-16 | 2001-09-26 | Tosoh Corp | ポリアルキルアミン誘導体からなる難燃助剤、これを用いた複合難燃剤及び難燃性樹脂組成物 |
JP4363764B2 (ja) | 2000-09-01 | 2009-11-11 | 三菱化学株式会社 | ポリカーボネート樹脂組成物 |
JP2002267019A (ja) | 2001-03-05 | 2002-09-18 | Honda Motor Co Ltd | 高温継手部用ガスケットおよびその製造方法 |
JP2002265799A (ja) | 2001-03-09 | 2002-09-18 | Canon Inc | 難燃性樹脂の製造方法、難燃性樹脂組成物及び成形品 |
DE10162532C1 (de) | 2001-12-19 | 2003-10-09 | Hilti Ag | Expandierbare Graphit-Intercalationsverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung |
US6746768B2 (en) * | 2001-12-26 | 2004-06-08 | Advanced Energy Technology Inc. | Thermal interface material |
WO2004038263A1 (ja) | 2002-10-08 | 2004-05-06 | Oiles Corporation | 球帯状シール体 |
-
2003
- 2003-09-25 EP EP03798498A patent/EP1559680B1/en not_active Expired - Lifetime
- 2003-09-25 US US10/528,155 patent/US7867615B2/en not_active Expired - Lifetime
- 2003-09-25 CN CNB038227800A patent/CN100351175C/zh not_active Expired - Lifetime
- 2003-09-25 WO PCT/JP2003/012256 patent/WO2004028967A1/ja active Application Filing
- 2003-09-25 JP JP2004539535A patent/JP4506465B2/ja not_active Expired - Lifetime
-
2009
- 2009-09-07 JP JP2009205957A patent/JP4656250B2/ja not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01252512A (ja) * | 1988-03-31 | 1989-10-09 | Union Kaabaito Services Kk | 改質黒鉛材 |
JPH10101316A (ja) * | 1996-09-30 | 1998-04-21 | Sekisui Chem Co Ltd | 可撓性グラファイト複合難燃組成物及び難燃シート |
JP4506465B2 (ja) * | 2002-09-26 | 2010-07-21 | オイレス工業株式会社 | 耐熱性膨張黒鉛シート |
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