CN1058000C - 双氨基苯硫酚类化合物,其合成方法及其应用 - Google Patents
双氨基苯硫酚类化合物,其合成方法及其应用 Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- -1 Bisaminothiophenol compound Chemical class 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 5
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 6
- 229920001971 elastomer Polymers 0.000 title abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000806 elastomer Substances 0.000 title abstract 2
- 239000011737 fluorine Substances 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical class NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 17
- 229920001973 fluoroelastomer Polymers 0.000 claims description 14
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical class C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920001897 terpolymer Polymers 0.000 claims description 8
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
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- 229910052794 bromium Inorganic materials 0.000 abstract description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 abstract description 3
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- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 abstract 1
- 229940116357 potassium thiocyanate Drugs 0.000 abstract 1
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- 238000001819 mass spectrum Methods 0.000 description 4
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- 238000001556 precipitation Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
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- PUWVBJGDOINCMQ-UHFFFAOYSA-N 4-(1,2,2,2-tetrafluoroethyl)aniline Chemical class NC1=CC=C(C(F)C(F)(F)F)C=C1 PUWVBJGDOINCMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920006169 Perfluoroelastomer Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
- C07C323/34—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a mercapto group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
2，2-双(4-氨基苯基)六氟丙烷能与硫氰酸钾和溴反应获得2，2-双(5-氨基-4，6-苯并噻唑基)六氟丙烷，该化合物可继续与氢氧化钾和盐酸反应得到2，2-双(4-氨基-3-巯基苯基)六氟丙烷，而此化合物是一种新的硫化剂，可应用于以CN基作交联基团的含氟弹性体中。
Description
本发明涉及一种双氨基苯硫酚化合物，特别是涉及有效地用作以腈基作为交联基团的含氟弹性体的固化试剂的双氨基苯硫酚。
下面这些双氨基苯硫酚类化合物是已知的并用作为耐热树脂聚苯并噻唑化合物等的原料。
本发明的目的是制备一种新的双氨基苯硫酚类化合物。它能有效地作为固化剂应用于以腈基作交联基团的含氟弹性体中。
根据本发明所提供的这种新的双氨基苯硫酚类化合物可用下面的通式[I]表示：
其中Rf是一个从C1到C10的全氟亚烷基(perfluoroalkylidene)。它可以盐的形式存在，比如盐酸盐，氢溴酸盐，硫酸盐，硼酸盐，羧酸盐等。
本发明中的双氨基苯硫酚类化合物可由以下一系列步骤合成：[III]-[II]的反应：在室温和搅拌下将溴的冰醋酸溶液滴加到双氨基苯基化合物[III]和碱金属的硫氰酸盐(其量超过双氨基苯基化合物[III]等摩尔量)的醋酸溶液中，这些硫氰酸盐可以是硫氰酸钠或硫氰酸钾。接着向其中加入水，将混和物加热到沸点，然后冷却过滤，将碳酸氢钠加入滤液中得到沉淀，即为双氨基苯并噻唑化合物[II]。反应机理可能是溴为氧化剂使硫氰酸根和芳环加成，接着氰硫基和氨基发生亲核环合反应
一般使用的双氨基苯基化合物[III]是2，2-双(4-氨基苯基)六氟丙烷。1，2-双(4-氨基苯基)四氟乙烷等也可使用。
[II]→[I]的反应
将此得到的双氨基苯并噻唑化合物[III]在约110℃到130℃，惰性气氛下加入到碱金属的氢氧化物(如氢氧化钠或氢氧化钾)水溶液中，然后将混合物慢慢升温到约260℃使反应进行，直到不产生氨为止。接着将温度降到约200℃。加入水后，使反应物冷却到室温，用无机酸如浓盐酸的稀水溶液加入反应混合物中，调节pH至6，最后加入冰醋酸到得到沉淀，为双氨基苯硫酚化合物(I)。
所获得的双氨基苯硫酚化合物及其盐可作为固化剂用于以氰基为交联基的含氟弹性体中。
用于本发明的含氟弹性体包括一种四氟乙烯、全氟(低级烷基乙烯基醚)或全氟(低级烷氧基-低级烷基乙烯基醚)和少量(即以三元共聚物计摩尔含量为0.1到5％)全氟不饱和腈化合物的三元共聚物。
全氟不饱和腈包括例如以下化合物：CF2＝CFO(CF2)nOCF(CF3)CN (n：2～5)CF2＝CF[OCF2CF(CF3)]nO(CF2)mCN (n：1～2，m：1～4)CF2＝CF[OCF2CF(CF3)]nCN (n：1～5)CF2＝CFO(CF2)nCN (n：1～10)
按重量计，以大约0.1到5份，最好是约1到3份双氨基苯硫酚化合物作为固化剂加到100份以CN基作交联基团的含氟弹性体中，这种可交联基团是由全氟不饱和腈化合物通过共聚作用而提供的。除了双氨基苯硫酚外该全氟弹性体还可容纳一些必须的添加剂，比如填料，增强剂，稳定剂，增塑剂，润滑剂，加工助剂等。将混和物放入轧制机或其它类似装置中捏和，并在约160℃到250℃的条件下初级硫化(加压硫化)约30～60分钟，然后在约200～300℃下进行二次硫化(烘炉硫化)约10～50小时，最好在惰性气氛中进行。
根据本发明，可以提供一种新的双氨基苯硫酚化合物作为硫化剂，它可有效应用于以CN作交联基团的含氟弹性体中。
下面将参考实例详细介绍本发明实施例1
将含有92.8g(0.58mol)的溴溶于20ml冰醋酸中，再将此溶液滴加入含有80g(0.24mol)2，2-双(4-氨基苯基)-六氟丙烷和120g(1.24mol)硫氰酸钾的280ml冰醋酸中的溶液中，在滴加过程中同时搅拌，该过程持续1小时。滴加完后，将混合物再搅拌2小时后，放置过夜。最后，向混和液中加1升水，并加热至沸，冷却过滤。
将碳酸氢钠加入滤液。然后再过滤得沉淀物，用水洗涤沉淀，干燥，就得到102g所需的2，2-双(5-氨基-4，6-苯并噻唑基)六氟丙烷。(产率：95％)熔点：262～266℃元素分析(C17H10F6N4S2)：计算值：C 45.53％，H 2.33％，F 25.45％，N 12.50％，S 14.28％实测值：C 45.23％，H 2.35％，F 24.87％，N 11.74％，S 13.80％质谱(MS)：448(相对强度86)M+
379(100)[M-CF3]+
310(15)[M-2CF3]+ 1’F NMR(δ：DMSO)：-15.2(s)(CF3COOH base)1H NMR(δ：DMSO)：H(1)，H(2)＝6.32ppm(AB q.)
JAB＝7.9Hz
H(3)＝6.72ppm(br.s.)
H(4)＝6.8ppm(br.s.)
H(1)∶H(2)∶H(3)∶H(4)＝1∶1∶1∶2实施例2
将120g(2.14mo1)氢氧化钾和16ml水加入圆底烧瓶中，在氩气氛中在120℃加热，同时搅拌混合物直至氢氧化钾全部溶于水中。然后将实施例1中的产物2，2-双(5-氨基-4，6-苯并噻唑基)六氟丙烷44.8g(0.1mole)加入上述溶液，亦在氩气中搅拌，同时将混和物慢慢加热到250℃。接着再搅拌20分钟。然后将混和物加热到260℃，并保持此温度10分钟，直到反应不再产生氨气。将反应温度降至200℃，慢慢加入600ml除去空气的水。再将混合物冷却至15℃。把由240ml浓盐酸在240ml除去空气的水中的稀水溶液加入反应物中，使pH为6，然后慢慢加入40ml冰醋酸，过滤得沉淀，水洗并干燥，即得最后产物37g 2，2-双(4-氨基-3-巯基苯基)六氟丙烷(产率：93％)。熔点：85℃元素分析(C15H12F4N2S2)：计算值：C 45.23％，H 3.01％，F 28.64％，N 7.03％，S 16.08％实测值：C 45.03％，H 2.88％，F 25.37％，N 5.79％，S 15.98％质谱(MS)：398M+，364[M-H2S]+，329[M-CF3]+
295[M-H2S-CF3]+ 1’F NMR(δ：DMSO·d6)：-14.55ppm(s)(CF3COOH base)1H NMR(δ)：H(1)，H(2)＝6.05ppm(AB q.)
JAB＝9Hz
H(HS)＝4.8ppm
H(H2N)＝6.14ppm实施例3
将200ml蒸馏水，3.3g全氟辛酸铵和2.3g KH2PO4加入净容量为500ml的不锈钢高压釜中，其内部气体为氮气所代替。使高压釜减压并降低到0℃。接着将下列化合物加到高压釜中
全氟(5-氰基戊基乙烯基醚)[CNVE] 6g
全氟(甲基乙烯基醚)[FWVE] 60g
四氟乙烯[TFE] 36g
然后将高压釜升温到60℃，把10ml含0.15g亚硫酸钠的水溶液和10ml含1.10g过硫酸铵的水溶液加入到高压釜中，使聚合反应进行16小时。
反应结束后，放出高压釜中未反应的气体。得到含水胶乳，将其放在冰箱中，使其在-30℃保持24小时而凝结。解冻后，固化的聚合物用50℃ 10％的乙醇洗涤，并在80℃下减压干燥6小时，即得75g三聚物(产率：74％)。红外分析结果表明在2266cm-1观察到CN基团的吸收峰，并且发现三元共聚物中含1.0％(mol)CNVE，57％(mol)FMVE和42％(mol)TFE。
将下列成份放入双辊橡胶磨中捏和，并在160℃初级硫化30分钟，在230℃下，氮气中二次硫化22小时。
三元共聚物 100份(重量〕
实施例1中的双氨基苯硫酚 1份
MT炭黑 5份
得到的硫化产物按JIS K-6301标准测试有以下标态性质：
硬度(JIS-A) 72
100％模量 52kg/cm2
抗张强度 148kg/cm2
已发现此双氨基苯硫酚化合物能有效地用作为以CN作交联基团的含氟弹性体的硫化剂。
Claims (10)
1.由通式[I]表示的双氨基苯硫酚化合物：
其中Rf为具有1到10个碳原子的全氟亚烷基。
2. 2，2-双(4-氨基-3-巯基苯基)六氟丙烷。
3.由通式[II]表示的双氨基苯并噻唑类化合物：其中Rf为具有1到10个碳原子的全氟亚烷基。
4.制备由通式[I]表示的双氨基苯硫酚类化合物的方法：其中Rf是具有1到10个碳原子的全氟亚烷基，所述方法包括由下式[II]表示的双氨基苯并噻唑化合物与碱金属的氢氧化物水溶液进行反应其中Rf与权利要求3所述定义相同。
5.一种用于含氟弹性体的硫化剂，所述含氟弹性体包括一种下述(a)、(b)和(c)化合物的三元共聚物，
(a)四氟乙烯，
(b)全氟(甲基乙烯基醚)、和
(c)全氟(5-氰基戊基乙烯基醚)，
所述硫化剂的特征在于，它包括式[I]表示的双氨基苯硫酚类化合物：
其中Rf为具有1到10个碳原子的全氟亚烷基。
6.根据权利要求5所述的硫化剂，其中，双氨基苯硫酚化合物为2，2-双(4-氨基-3-巯基苯基)六氟丙烷。
7.权利要求5或6所述的硫化剂，其中所述含氟弹性体是(a)四氟乙烯、(b)全氟(甲基乙烯基醚)和(c)全氟(5-氰基戊基乙烯基醚)的三元共聚物。
8.一种可硫化的含氟弹性体组合物，所述组合物包括：
含氟弹性体，它包含(a)四氟乙烯、(b)全氟(甲基乙烯基醚)和全氟(5-氰基戊基乙烯基醚)的三元共聚物；以及，
式[I]表示的双氨基苯硫酚类化合物：
其中Rf是具有1到10个碳原子的全氟亚烷基。
9.根据权利要求8所述的可硫化含氟弹性体组合物，其中，双氨基苯硫酚化合物是2，2-双(4-氨基-3-巯基苯基)六氟丙烷。
10.根据权利要求8或9中所述的可硫化含氟弹性体组合物，其中，所述含氟弹性体是(a)四氟乙烯、(b)全氟(甲基乙烯基醚)和(c)全氟(5-氰基戊基乙烯基醚)的三元共聚物。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP308199/1994 | 1994-11-17 | ||
| JP6308199A JPH08143535A (ja) | 1994-11-17 | 1994-11-17 | ビスアミノチオフェノール化合物、その製造法およびそれよりなる含フッ素エラストマー用硬化剤 |
| JP308199/94 | 1994-11-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1132200A CN1132200A (zh) | 1996-10-02 |
| CN1058000C true CN1058000C (zh) | 2000-11-01 |
Family
ID=17978116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95119728A Expired - Fee Related CN1058000C (zh) | 1994-11-17 | 1995-11-17 | 双氨基苯硫酚类化合物,其合成方法及其应用 |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US5672758A (zh) |
| EP (1) | EP0712842B1 (zh) |
| JP (1) | JPH08143535A (zh) |
| CN (1) | CN1058000C (zh) |
| DE (1) | DE69507001T2 (zh) |
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| US6191208B1 (en) * | 1998-05-20 | 2001-02-20 | Dupont Dow Elastomers L.L.S. | Thermally stable perfluoroelastomer composition |
| EP1114094B1 (en) | 1998-08-10 | 2004-07-14 | Dupont Dow Elastomers L.L.C. | Curable perfluoroelastomer composition |
| US6281296B1 (en) | 1998-08-10 | 2001-08-28 | Dupont Dow Elastomers L.L.C. | Curable perfluoroelastomer composition |
| WO2005000917A1 (en) * | 2003-01-29 | 2005-01-06 | Greene, Tweed Of Delaware, Inc. | Bisaminopehnyl-based curatives curatives and amidine-based curatives and cure accelerators for perfluoroelastomeric compositions. |
| EP1587784B1 (en) | 2003-01-29 | 2014-10-15 | Greene, Tweed Of Delaware, Inc. | Bisaminophenyl-based curatives and amidine-based curatives and cure accelerators for perfluoroelastomeric compositions |
| US7514506B2 (en) * | 2004-03-31 | 2009-04-07 | Greene, Tweed Of Delaware, Inc. | Fast curing fluoroelastomeric compositions, adhesive fluoroelastomeric compositions and methods for bonding fluoroelastomeric compositions |
| CN1297536C (zh) * | 2005-06-02 | 2007-01-31 | 上海交通大学 | 取代二(氨基巯基)苯盐酸盐的制备方法 |
| CN101880251B (zh) * | 2010-02-05 | 2013-03-20 | 厦门大学 | 4，4’-二巯基偶氮苯及其制备方法 |
| JP5833657B2 (ja) | 2010-09-24 | 2015-12-16 | グリーン， ツイード オブ デラウェア， インコーポレイテッド | 高温への適用に適したフッ素含有エラストマー組成物 |
| US9365712B2 (en) | 2010-09-24 | 2016-06-14 | Greene, Tweed Technologies, Inc. | Fluorine-containing elastomer compositions suitable for high temperature applications |
| CN105324412B (zh) | 2013-06-27 | 2017-07-18 | 3M创新有限公司 | 含氟聚醚‑聚硅氧烷弹性体组合物和成型制品 |
| EP3107950A1 (en) | 2014-02-19 | 2016-12-28 | 3M Innovative Properties Company | Hybrid fluoroelastomer composition, curable composition, and methods of making and using the same |
| CN104672726B (zh) * | 2015-03-11 | 2016-11-09 | 江苏千富之丰科技有限公司 | 一种免二次硫化氟弹性体及其制备方法 |
| EP3601426B1 (en) * | 2017-03-31 | 2023-05-24 | Solvay Specialty Polymers Italy S.p.A. | Method of making cured parts |
| EP3601427B1 (en) * | 2017-03-31 | 2023-05-10 | Solvay Specialty Polymers Italy S.p.A. | Fluoroelastomer composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0606883A1 (en) * | 1993-01-14 | 1994-07-20 | Nippon Mektron, Ltd. | Fluorine-containing elastomer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0477587A (ja) * | 1990-07-13 | 1992-03-11 | Hitachi Ltd | 低粘度ワニスとそれを用いた電子装置の製法 |
| US5223599A (en) * | 1992-04-10 | 1993-06-29 | Uniroyal Chemical Company, Inc. | Polyurethane elastomer and non-pneumatic tire fabricated therefrom |
| JPH08104789A (ja) * | 1994-10-04 | 1996-04-23 | Nippon Mektron Ltd | 含フッ素エラストマー組成物 |
-
1994
- 1994-11-17 JP JP6308199A patent/JPH08143535A/ja active Pending
-
1995
- 1995-09-27 DE DE69507001T patent/DE69507001T2/de not_active Expired - Fee Related
- 1995-09-27 EP EP95115263A patent/EP0712842B1/en not_active Expired - Lifetime
- 1995-10-31 US US08/550,870 patent/US5672758A/en not_active Expired - Lifetime
- 1995-11-17 CN CN95119728A patent/CN1058000C/zh not_active Expired - Fee Related
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1996
- 1996-11-25 US US08/753,407 patent/US5688872A/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0606883A1 (en) * | 1993-01-14 | 1994-07-20 | Nippon Mektron, Ltd. | Fluorine-containing elastomer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1132200A (zh) | 1996-10-02 |
| DE69507001D1 (de) | 1999-02-11 |
| EP0712842A1 (en) | 1996-05-22 |
| US5688872A (en) | 1997-11-18 |
| DE69507001T2 (de) | 1999-06-10 |
| US5672758A (en) | 1997-09-30 |
| EP0712842B1 (en) | 1998-12-30 |
| JPH08143535A (ja) | 1996-06-04 |
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