公开(公告)号：JPH03190829A

公开(公告)日：1991-08-20

申请号：JP32841789

申请日：1989-12-20

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  OE TADAYUKI ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO

IPC: B01J31/02 ,  C07B61/00 ,  C07C2/46 ,  C07C2/64 ,  C07C13/465

Abstract: PURPOSE:To obtain an indane derivative useful as an intermediate for industrial chemicals, a curing agent for various resins, etc., in high yield without causing side reactions such as sulfonation by reacting a benzene derivative with isoprene using alkanesulfonic acids as a catalyst. CONSTITUTION:A compound expressed by formula I (R1 and R2 are H or 1-4C alkyl) is blended with isoprene using a compound expressed by formula II (R3 is 1-8C straight chain or branched chain or alicyclic alkyl) as a catalyst at 20-50 deg.C for 1-10hr and the blend is stirred for 1-4hr. Thereby the compound expressed by formula I is reacted with isoprene to provide the compound expressed by formula III. The raw material and product are not sulfonated and liquid-solid separation in neutralization and cleaning is remarkably improved, because sulfuric acid is not used in the above-mentioned method. Further, cooling energy is not required, because it is not necessary to carry out the reaction at low temperature. The alkanesulfonic acid can be reused.

公开(公告)号：JPH03184942A

公开(公告)日：1991-08-12

申请号：JP32267689

申请日：1989-12-14

Applicant: MITSUI TOATSU CHEMICALS

Inventor： OE TADAYUKI ,  MATSUO MITSUKI ,  YAMAGUCHI TERUHIRO

IPC: C07C201/06 ,  C07C209/32 ,  C07C209/68 ,  C07C211/09 ,  C07C211/49

Abstract: NEW MATERIAL:1,3-Diamino-2,4-diisopropylbenzene. USE:A raw material for isocyanates, epoxy resins, bismaleimides etc., or a curing agent giving moderate curing rate esp. when used as a curing agent for urethane RIM. PREPARATION:A 3,5-diisopropyl-1,2-dihalogenobenzene selectively prepared by diisopropylation between (A) an o-dihalogenobenzene and (B) an isopropyl halide, propylene or isopropanol is put to dinitration followed by reduction- dehalogenation, thus easily obtaining the objective 1,3-diamino-2,4- diisopropylbenzene in high efficiency. When the present compound is used for urethane RIM, films with excellent physical properties can be produced in good formability.

公开(公告)号：JPH07292105A

公开(公告)日：1995-11-07

申请号：JP31388794

申请日：1994-12-19

Applicant: MITSUI TOATSU CHEMICALS

Inventor： YAMASHITA WATARU ,  SAKATA YOSHIHIRO ,  OKAWA YUICHI ,  TAMAI MASAJI ,  ISHIDA TSUTOMU ,  MATSUO MITSUKI ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO

IPC: C07D213/69 ,  C08G73/10 ,  C08J5/06 ,  C08J5/08 ,  C08J5/18

Abstract: PURPOSE:To obtain a thermoplastic polyimide provided with colorless transparency, low dielectric property and thermal stability, capable of being melt-molded, and useful as an electric/electronic material, an optical material, etc. CONSTITUTION:A polyimide contains one or more kinds of repeating structural units of formula I (Ar is a tetravalent noncondensed polycyclic aromatic group connected to a 6-27C aromatic group; the trifluoromethyl group is substituted at the 3 or 4-position of the pyridine nucleus; the N of the imide is bound to the 3 or 4-position based on the ether bond) as essential constituting units. The polyimide is obtained by reacting an aromatic diamine of formula II (the amino group is substituted to the 3 or 4-position based on the ether bond) with a tetracarboxylic acid dianhydride of formula III and subsequently subjecting the obtained polyamic acid to a thermal or chemical imidation reaction.

公开(公告)号：JPH0726018A

公开(公告)日：1995-01-27

申请号：JP17042993

申请日：1993-07-09

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO ,  YAMASHITA WATARU ,  OKAWA YUICHI ,  OIKAWA HIDEAKI ,  ASANUMA TADASHI

IPC: C07C211/49 ,  C07C217/82 ,  C07C323/18 ,  C07C323/37 ,  C08G73/10

Abstract: PURPOSE:To produce a polyimide improved in moldability by reacting a specific arom. diamine, a tetracarboxylic dianhydride, and arom. dicarboxylic anhydride and/or an arom. monoamine and imidating the resulting polyamic acid. CONSTITUTION:A polyimide comprising repeating structural units of formula IV and having molecular terminals substd. by groups nonreactive with a dicarboxylic anhydride or amine is produced by adding, to an org. solvent (e. g. m-cresol), 1.0mol of an arom. diamine of formula I (wherein X and Y are each O, S, or methylene) {e. g. 1,3-bis[4-(4-aminophenoxy)phenoxy]benzene), 0.9-1.0mol of a tetracarboxylic dianhydride of formula II (wherein R is a tetravalent, 6-27C monocyclic or condensed polycyclic arom. group) (e.g. pyromellitic dianhydride), and 0.001-1.0mol of an acid anhydride of formula III (wherein Z1 is a divalent, 6-15C aliph. or monocyclic arom. group), stirring and reacting those reactants under heating in an N2 atmosphere to form a polyamic acid, and imidating the polyamic acid at 100-400 deg.C.

公开(公告)号：JPH06271516A

公开(公告)日：1994-09-27

申请号：JP5697893

申请日：1993-03-17

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  ISHIDA TSUTOMU ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO

IPC: C07C213/06 ,  C07C217/90

Abstract: PURPOSE:To provide a novel colorless and transparent fluorinecontaining aromatic diamine having a low dielectric constant and useful as a starting raw material for polyimides, polyamides, polyamideimides, bismaleimides and epoxy resins excellent in moldability. CONSTITUTION:A fluorine-containing aromatic diamine of formula I or II. It is obtained by condensing a trifluoromethyl benzene derivative of formula III (X is halogen or nitro substituted at 3,5 or 2,4 positions based on CF3) with 3-amino-5-trifluoromethylphenol of formula IV in an aprotic solvent in the presence of a base. A polyimide containing the diamine of formula I or II as monomer units exhibits various good physical characteristics including high heat resistance, high melt flovability originated from the existence of the amino group at the meta position to the bond group, low dielectric constant and colorless transparency originated from the CF3 group. Since the CF3 group is placed at the meta position to the amino group, the lowering in the polymerization degree is not caused by electronic factors.

公开(公告)号：JPH06207015A

公开(公告)日：1994-07-26

申请号：JP8425193

申请日：1993-04-12

Applicant: MITSUI TOATSU CHEMICALS

Inventor： YAMASHITA WATARU ,  SAKATA YOSHIHIRO ,  KATAOKA TOSHIYUKI ,  OKAWA YUICHI ,  OIKAWA HIDEAKI ,  ASANUMA TADASHI ,  MATSUO MITSUKI ,  ISHIDA TSUTOMU ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO

IPC: C08G73/10 ,  C08J5/18 ,  C09K3/00

Abstract: PURPOSE:To obtain a polyimide having low permittivity, good processability, good heat resistance, etc., by reacting a specified aromatic diamine with a tetracarboxylic acid in the presence of a specified compound to give a polyamic acid and imidating the polyamic acid. CONSTITUTION:An aromatic diamine composed mainly of an aromatic diamine compound of formula I {wherein X1 is a direct linkage or a divalent group comprising O, CO or C(CH3)2; Ar is a divalent group of formula II, III or IV [wherein X2 is a direct linkage or a divalent group comprising O, S, CO or C(CH3)2; m is 1 to 6; and p is 0 or 1 to 4, provided that P is 1 to 4 when n is 0 in formula I]; m is 1 to 6; and n is 0 or 1 to 4} is reacted with a tetracarboxylic acid dianhydride consisting mainly of a compound of formula V (wherein R is a tetravalent group selected from among noncondensed polycyclic aromatic groups having 2-27C aliphatic groups, condensed polycyclic aromatic groups, aromatic groups, etc., linked to each other directly or through a crosslinking member) to give a polyamic acid. This polyamic acid is thermally or chemically imidated to give a polyimide having repeating structural units of formula VI (wherein X1, Ar, m, n and R are each as defined above).

公开(公告)号：JPH06100506A

公开(公告)日：1994-04-12

申请号：JP24787292

申请日：1992-09-17

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  ISHIDA TSUTOMU ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO

IPC: C07C213/06 ,  C07C217/90

Abstract: PURPOSE:To obtain new 1,3-bis(3-aminophenoxy)-4-trifluoro-methylbenzene useful as a starting raw material for polyimide, polyamide, polyamideimide, bismaleimide and epoxy resins. CONSTITUTION:1,3-Bis(3-aminophenoxy)-4-trifluoromethylbenzene of formula I. The compound of formula I is obtained by condensing 2,4- dichlorobenzotrifluoride of formula II with m-aminophenol in the presence of a base in an aprotic solvent. The aromatic diamine of formula I is extremely useful as a raw material for colorless and transparent polyimides having a low dielectric constant and excellent moldability.

公开(公告)号：JPH05286907A

公开(公告)日：1993-11-02

申请号：JP8546692

申请日：1992-04-07

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO

IPC: C07C201/12 ,  C07C205/12 ,  C07C205/38 ,  C07C213/02 ,  C07C217/90

Abstract: PURPOSE:To obtain an aromatic dinitro compound and an aromatic diamino compound having new trifluoromethyl and biphenyl structure usable as a starting raw material for polyimide, polyamide, polyamide-imide, bismaleimide and epoxy resins. CONSTITUTION:4,4'-Bis(3-nitro-5-trifluoromethylphenyloxy)biphenyl of formula I and 4,4'-bis(3-amino-5-trifluoromethylphenyloxy)biphenyl of formula II. The aromatic dinitro compound of formula I is obtained by condensing 3,5- dinitrobenzotrifluoride with biphenol in the presence of a base in an aprotic polar solvent. The aromatic diamino compound of formula II is obtained by reducing the new aromatic dinitro compound of formula I. The compounds of formula I and formula II are useful as a raw material for polyimides having low dielectric characteristics and excellent moldability and processability.

公开(公告)号：JPH05178796A

公开(公告)日：1993-07-20

申请号：JP16902192

申请日：1992-06-26

Applicant: MITSUI TOATSU CHEMICALS

Inventor： MATSUO MITSUKI ,  YAMAGUCHI KEISABURO ,  YAMAGUCHI TERUHIRO ,  OE TADAYUKI

IPC: B01J31/22 ,  C07B61/00 ,  C07C201/12 ,  C07C205/38

Abstract: PURPOSE:To efficiently obtain the subject compound useful as a raw material for producing a polyimide having low dielectric constant, excellent moldability and processability by subjecting 3,5-dinitrotrifluoromethylbenzene to self condensation reaction in the presence of a nitrite in an aprotic polar solvent. CONSTITUTION:3,5-Dinitrotrifluoromethylbenzene of formula I is reacted in the presence of a nitirde (e.g. sodium nitrite) in an aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone in a reactor under heating while introducing a nitrogen gas under stirring at 130 deg.C for 10 hours. The reaction mixture is discharged into water, precipitated solid constituted is filtered and dried to give a crude reactional product. Then the crude reactional product is purified by sludging with methanol to give the objective compound of formula II useful as an intermediate for 3,3'-diamino-5,5'-bis(trifluoromethyl)diphenyl ether useful as a raw material of producing polyimides, etc.

公开(公告)号：JPH04261422A

公开(公告)日：1992-09-17

申请号：JP2177891

申请日：1991-02-15

Applicant: MITSUI TOATSU CHEMICALS

Inventor： OE TADAYUKI ,  MATSUO MITSUKI ,  YAMAGUCHI TERUHIRO

IPC: C08G63/02 ,  C07C69/675 ,  C08G63/00

Abstract: PURPOSE:To provide the subject polyester compounds having a specified structure and excellent in mold release characteristics as a release agent for thermosetting resins, i.e., free from stain of a mold, deterioration of coating properties thereof and reduction of physical properties of moldings. CONSTITUTION:Polyester compounds represented by formula I (m+m=13 or 15; r and s are 0-7 and sum of them is 1-7; Sum of j and k is 1; R1 is H or 1-4C alkyl) or formula II (m, n, r and s are same in formula I; R2 and R3 are H or 1-4C alkyl). The above-mentioned compounds have 1000-8000 average molecular weight and 5-70 hydroxyl number and can be obtained by reacting a hydroxy fatty acid or its fatty alcohol ester with a glycol.