Nippon Mektron Limited

Unimatec Co., Ltd

Takehiro Sonoi

Haruyoshi Tatsu

Satoru Saito

Okimasa Yamada

Toshimasa Sagawa

Valerii Romanovich Polishchuk, Deceased

Tetsuya Mizuno

Katsuyuki Sato

Keisuke Kokin

Lev Solomonovich German, Deceased

Sergei Rafailovich Sterlin

Kimihiko Urata

Toshio Kubota

Victor Filippovich Cherstokov

Nina Ivanovna Delyagina

Sunao Ikeda

Lev Solomonovich, Deceased

Futoshi Masaki, Deceased

Futoshi Masaki

Kenji Iimura

Leng-Tain Lin

Provided is a fluorine-containing diblock copolymer having good water and oil repellency by using, as a raw material, a fluorine-containing (meth)acrylic ester having low bioaccumulation potential. The fluorine-containing diblock copolymer is produced by: process (A) a process for producing a fluorine-containing diblock copolymer by polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1) in the presence of a trithiocarbonic ester compound and a radical polymerization initiator and then polymerizing a non-fluorine vinyl-based monomer, or process (B) a process for producing a fluorine-containing diblock copolymer by polymerizing a non-fluorine vinyl-based monomer in the presence of a trithiocarbonic ester compound and a radical polymerization initiator and then polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1). 

Fluorine-containing diblock copolymer

Provided is a fluorine-containing macroinitiator, particularly a fluorine-containing macroinitiator that enables production of a fluorine-containing block copolymer containing a non-fluorine vinyl-based monomer having a long side chain. The fluorine-containing macroinitiator includes a polymer represented by the following formula (1) and having a number-average molecular weight of 3,000 to 100,000. In the following formula (1), R, Rand Rare each a specific group, and Q is a polymer segment composed of a structural unit represented by the following formula (2). In the following formula (2), Ris a hydrogen atom or a methyl group, Rf is a fluoroalkyl group having a specific structure, and k is an appropriate integer that is not 0. 

Fluorinated-containing macroinitiator and production process for the same

An iodine-containing fluoropolyether represented by the following general formula [I]:RfO[CF(CF)CFO]CF(CF)(CH)I&#x2003;&#x2003;[I](where Rf is a perfluoroalkyl group having 1-3 carbon atoms, m is an integer of 0-10, and n is an integer of 3-12), is a novel compound having a perfluoropolyetheralkyl group capable of giving a flexibility to the molecule chain through the etheral bond, said perfluoropolyether alkyl group being bonded to the alkyl iodide having an alkyl group having 3 or more carbon atoms, and can be produced by reaction of a fluoropolyether group-containing alcohol represented by the following general formula [II]:RfO[CF(CF)CFO]CF(CF)(CH)OH&#x2003;&#x2003;[II](Where Rf, m, and n have the same meanings as defined above) with a metal iodide, preferably potassium iodide.

Iodine-containing fluoropolyether and process for producing the same

In the production of 2,2,3,3-tetrafluorooxethane by reaction of tetrafluoroethylene with a compound of formaldehyde generation source in anhydrous hydrogen fluoride, the reaction is carried out in the presence of polyfluoroalkylcarboxylic acid or polyfluoroalkyl ester thereof, represented by the following general formula RfCOORf' (where Rf is a polyfluoroalkyl group having 1-5 carbon atoms, and Rf&#x2032; is a hydrogen atom or a polyfluoroalkyl group having 1-5 carbon atoms), preferably CFCOOH, CFCOOCHCFCF, or CFCOOCHCF, whereby a high reaction yield can be attained.

Process for producing 2,2,3,3,-tetrafluorooxetane

An alkylamino group-terminated fluoroether compound, represented by the following general formula:RfO[CF(CF)CFO]CF(CF)(CH)NRR(where Rf is a perfluoro lower-alkyl group, Ris an alkyl group having 1-12 carbon atoms, Ris a hydrogen atom, or an alkyl group having 1-12 carbon atoms, m is an integer of 0-10, and n is an integer of 3-8) is a novel compound, and is produced by reaction of an iodide-terminated fluoroether compound, represented by the following general formula:RfO[CF(CF)CFO]CF(CF)(CH)Iwith an alkylamine compound, represented by the following general formula:NHRR.

Alkylamino group-terminated fluoroether and process for producing the same

2.2'-bis(3-mercaptophenyl)hexafluoropropane [bisthio-phenol AF] is obtained in good yield by chlorosulfonating 2.2'-bisphenylhexafluoropropane and reducing the thus quantitatively obtained 2,2'-bis(3-chlorosulfonylphenyl)-hexafluoropropane with zinc under acidic conditions and is effectively used as a cross-linking agent for a fluorine-containing elastomer having halogenophenyl groups as cross-linkable groups.

Process for producing bisthiophenolperfluoroalkylidene compound

2,2 bis(3-mercaptophenyl)hexafluoropropane �bisthiophenol AF! is obtained in good yield by chlorosulfonating 2,2'-bisphenylhexafluoropropane and reducing the thus quantitatively obtained 2,2'-bis(3-chlorosulfonylphenyl)hexafluoropropane with zinc under acidic conditions and is effectively used as a cross-linking agent for a fluorine-containing elastomer having halogenophenyl groups as cross-linkable groups.

Crosslinkable composition of fluoroelastomer and

A fluorine-containing elastomer composition, which comprises a terpolymer of tetrafluoroethylene, perfluoro(lower alkyl vinyl ether) or perfluoro (lower alkoxy-lower alkyl vinyl ether) and cross-linkable cyano group-containing (perfluorovinylether), and a bis(aminothiophenol) compound represented by the following general formula as a cross-linking agent: ##STR1## wherein A is an alkylidene group having 1 to 6 carbon atoms, a perfluoroalkylidene group having 1 to 10 carbon atoms, a SO.sub.2 group, an O atom, a CO group or a carbon-carbon bond capable of directly bonding two benzene rings and one of X and Y is an amino group, while the other is a mercapto group, can produce cross-linked fluororubber moldings having an improved compression set.

Fluorine-containing elastomer composition

Heptafluoroisobutenyl methyl ether having the following formula: ##STR1## is oxidized with ozone to produce perfluoro(2-methyl-1,2-epoxy-propyl) methyl ether. The resulting intermediate compound is allowed to react with an aromatic compound ArH to produce .alpha.,.alpha.-bis(trifluoromethyl)arylacetic acid methyl ester having the following formula: ##STR2## By hydrolysis, decarboxylation and further hydrolysis of the ester compound, .alpha.,.alpha.-bis(trifluoromethyl)arylacetic acid for use as raw materials for medicines, agricultural chemicals, liquid crystals, etc. or reagents for determining an optical purity can be obtained.

.alpha.,.alpha.-bis(trifluoromethyl)arylacetic acid ester; its

(1) CF.sub.2 .dbd.CFO(CF.sub.2).sub.n COOR is allowed to react with chlorine or bromine to obtain CF.sub.2 XCFXO(CF.sub.2).sub.n COOR', (2) which is allowed to react with a Grignard reagent MgBrC.sub.6 H.sub.3 (CH.sub.3).sub.2 to convert the terminal group to --COC.sub.6 H.sub.3 (CH.sub.3).sub.2, (3) followed by reaction with diethylaminosulfur trifluoride to convert --COC.sub.6 H.sub.3 (CH.sub.3).sub.2 to --CF.sub.2 C.sub.6 H.sub.3 (CH.sub.3).sub.2, (4) followed further by oxidation of the resulting methyl group and by esterification to convert the methyl group to --CF.sub.2 C.sub.6 H.sub.3 (COOR).sub.2 and (5) followed by dechlorination or debromination to obtain CF.sub.2 .dbd.CFO(CF.sub.2).sub.n CF.sub.2 C.sub.6 H.sub.3 (COOR).sub.2. The resulting bifunctional vinyl ether compound having an aromatic ring is a novel compound and can be used as a copolymer component for fluorine-containing elastomers.

Vinyl compound, its synthetic intermediates and processes for producing

2,2-bis(4-aminophenyl)hexafluoropropane is allowed to react with potassium thiocyanate and bromine to obtain 2,2-bis(5-amino-4,6-benzothiazolyl)hexafluoropropaneo which is allowed to further react successively with potassium hydroxide and hydrochloric acid to obtain 2,2-bis(4-amino-3-mercapto-phenyl)hexafluoropropane, which is a novel compound applicable as a curing agent for a fluorine-containing elastomer having CN groups as cross-linkable groups.

Bisaminothiophenol compound, process for producing the same and curing

2,2-bis(4-aminophenyl)hexafluoropropane is allowed to react with potassium thiocyanate and bromine to obtain 2,2-bis (5-amino-4,6-benzothiazolyl)hexafluoropropane, which is allowed to further react successively with potassium hydroxide and hydrochloric acid to obtain 2,2-bis(4-amino-3-mercaptophenyl)hexafluoropropane, which is a novel compound applicable as a curing agent for a fluorine-containing elastomer having CN groups as cross-linkable groups.

.alpha.-(trifluoromethyl)arylacetic acid for use as raw materials for medicines, agricultural chemicals, liquid crystals etc. or reagents for determining an optical purity is readily obtained through very simple reaction steps, i.e. by reacting a perfluoro(2-methyl-1,2-epoxypropyl)ether compound obtainable by ozone, oxidation of a heptafluoroisobutenyl ether compound with an aromatic compound ArH to afford an .alpha.,.alpha.-bis(trifluoromethyl)arylacetic acid ester, followed by decarboxylation and hydrolysis of the resulting ester compound.

Process for producing .alpha.-(trifluoromethyl)arylacetic acid

A composition for low hardness, fluorine-containing rubber comprising solid fluorine-containing rubber, liquid fluorine-containing rubber, an aliphatic amine having an alkyl group having at least 8 carbon atoms and a perfluoropolyether has a good mold releasability at the vulcanization molding and can produce a vulcanized product having a JIS A hardness, according to JIS K-6301, of not more than 50 and less adhesiveness to a metal.

Composition for low hardness, fluorine-containing rubber

Hexafluoroacetone or its hydrate is produced in a higher yield than that of the conventional process (1) by oxidizing a heptafluoroisobutenyl ether with ozone or (2) by thermally decomposing an octafluoroisobutyl ether or a heptafluoroisobutenyl ether in the presence of oxygen and an activated carbon catalyst.

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Kitaibaraki, Japan

Takehiro Sonoi