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公开(公告)号:FR1415977A
公开(公告)日:1965-10-29
申请号:FR993361
申请日:1964-10-30
Applicant: BASF AG
Inventor: POMMER HORST , STILZ WALTER , HANTGE HARTMUT , ROSENKRANZ MAGNUS
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公开(公告)号:GB920988A
公开(公告)日:1963-03-13
申请号:GB2780160
申请日:1960-08-11
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST , KOENIG KARL-HEINZ
IPC: C07C17/26 , C07C25/24 , C07D317/50 , C07F9/40
Abstract: Compounds of the 1,4-bis-(styryl)-benzene series are prepared by reacting a benzylphosphonic acid which is not substituted in paraposition by a free or esterified carboxylic acid group and whose carbon atom attached to the phosphorus atom bears at least one hydrogen atom, or an ester of the same, with a 1,4-diacylbenzene (acyl includes -CHO) in the presence of a proton acceptor. An inert solvent, especially a polar solvent, may be used. The phosphonic compound may be of formula where R, R1, R2 and R3 may be hydrogen, aliphatic groups, especially alkyl, halogen, free, esterified or etherified hydroxy, sulphonic acid, sulphonic acid amide, nitrile, carboxylic amide, or, except for R, free or esterified carboxylic groups. R and R1, R and R2 or R and R3 may also be members of 5- or 6-membered cyclic diethers annellated with the benzene ring through the oxygen atoms, the carbon atoms in the ether rings being substituted if desired. R4, R5 and R6 may be hydrogen or aliphatic, especially alkyl, groups; R5 and R6 may also be aryl or may be linked in a ring with the phosphorus. The benzene ring may form part of a naphthalene system. Carboxylic amide groups may be N-substituted, e.g. by C1-6 alkyl or by alkylene completing a ring with the nitrogen. The diacylbenzenes may be of formula where R7, R8 and R9 may be hydrogen, or aliphatic or araliphatic, especially alkyl, groups. R7 and R8 may also be halogen, free, etherified or esterified hydroxy, or sulphonic acid groups. The bis-(styryl)-benzenes may be of use as optical bleaches for synthetic and natural macromolecular substances, and as light protective agents, stabilizers, pesticides and dyes. Examples describe the preparation of: 1,4-bis-(31,41-methylenedioxystyryl)benzene; 1,4-bis-(m- and p-cyanostyryl)benzenes; 1,4-bis - (p - methoxystyryl)benzene; 1,4-bis-(31,41-dichlorostyryl)benzene; 1,4-bis(p-chlorostyryl) benzene; 1,4-bis(21,41-dichlorostyryl)benzene; and 1,4-distyryl-2,5-dichlorobenzene. The diethyl esters of the following benzylphosphonic acids are prepared as starting materials from triethyl phosphite and appropriate benzyl halides: 3,4-methylenedioxybenzyl; m- and p-cyanobenzyl; p-methoxy-benzyl; 3,4-dichlorobenzyl; p-chlorobenzyl; and 2,4-dichlorobenzyl phosphonic acids.
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公开(公告)号:GB913735A
公开(公告)日:1962-12-28
申请号:GB2195360
申请日:1960-06-23
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST , WOLFF ERIKA , FESSMANN HEINZ
Abstract: A macromolecular organic substance contains for the homogeneous optical brightening thereof at least one compound of the 1,4-bis-styryl benzene series having the general formula in which R1 and R11 denote carboxyl groups carboxylic acid ester or amide groups or nitrile groups, R2 and R3 denote hydrogen, halogens, alkyl groups, aralkyl groups or alkoxy groups, and in which R1 and R11 may be identical or different and symmetrically or unsymmetrically attached to the benzene rings, and R2 and R3 may be identical or different. Specified macromolecular substances are polyamides, polyesters, aminoplasts, rubbers, regenerated cellulose, polymers and copolymers of styrene, vinyl chloride, vinylidene chloride, butadiene, acrylamide and acrylonitrile, polyethylene, polypropylene, polyisobutylene and polyformaldehyde. In the Examples:- (1) a mixture of caprolactam and hexamethylene diammonium adipate is polymerized in the presence of 1,4-bis-(p-carbomethoxystyryl)-benzene; (2) caprolactam is polymerized in the presence of titanium dioxide and 1,4-bis-(p-cyanostyryl)-benzene; (3) hexamethylene diammonium adipate is polymerized in the presence of 1,4-bis-(m-carbomethoxystyryl) benzene; (4) sebacic acid and hexamethylene diamine are polymerized in the presence of 1,4-bis-(p-carbomethoxystyryl)-benzene; (5) polycaprolactam is mixed with 1,4-bis-(p-cyanostyryl)-benzene and ditertiary-butyl-p-cresol; (6) polypropylene is mixed with 1,4-bis-(p-cyanostyryl)-benzene; (7) dimethyl terephthalate and ethylene glycol are polymerized in the presence of zinc acetate, antimony trioxide and 1,4-bis-(p-carbomethoxystyryl)-benzene; (8) polypropylene is mixed with titanium dioxide and 1,4-bis-(p-carbomethoxystyryl)-benzene; (9) dimethyl terephthalate and ethylene glycol are polymerized in the presence of antimony trioxide, zinc acetate and 1,4-bis-(p-cyanostyryl)-benzene and (10) polyformaldehyde impregnated with a solution of a polyamide made from hexamethylene diammonium adipate, p-diamino-dicyclohexylmethane adipate, caprolactam and 2,21-methylene-bis-(4-ethyl-6-t-butyl phenol) is mixed with (a) 1,4-bis-(41-carbomethoxystyryl)-benzene, (b) bis-(41-cyanostyryl)-benzene. Specification 813,539 is referred toALSO:1,4-bis-styrylbenzenes of the formula: wherein R1 and R11 are identical or different and may be carboxyl groups, esterified carboxyl groups, nitrile groups, or carboxylic amide groups are made by reacting a m or p-benzyl halide derivative of the formula with a triarylphosphine to form triaryl-cyano benzylphosphonium chloride, 2 mols of which are reacted in the presence of an alkaline condensing agent with one mol of a terephthaldehyde of the general formula where R2 and R3 which may be the same or different are hydrogen, halogens, alkyl groups, aralkyl groups or alkoxy groups. Examples describe the preparation of 1,4-bis-(p-carbomethoxystyryl)benzene; 1,4-bis-(p-cyanostyryl) benzene; 1,4-bis(m-cyanostyryl)benzene; and 1,4 - bis(m-carbomethoxystyryl)benzene. Specification 813,539 is referred to.
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公开(公告)号:BE609585A
公开(公告)日:1962-04-25
申请号:BE609585
申请日:1961-10-25
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST , SCHMIDT FRANZ , BICZYSKO HANS , FESSMANN HEINZ
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25.
公开(公告)号:BE601649A
公开(公告)日:1961-09-22
申请号:BE601649
申请日:1961-03-22
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST
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26.
公开(公告)号:BE600637A
公开(公告)日:1961-08-24
申请号:BE600637
申请日:1961-02-24
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST
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公开(公告)号:FR1265005A
公开(公告)日:1961-06-23
申请号:FR835745
申请日:1960-08-12
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST , KCENIG KARL-HEINZ
IPC: C07C17/26 , C07D317/50 , C07F9/40
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公开(公告)号:FR1242405A
公开(公告)日:1960-09-30
申请号:FR806602
申请日:1959-10-02
Applicant: BASF AG
Inventor: STILZ WALTER , POMMER HORST
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公开(公告)号:CA771076A
公开(公告)日:1967-11-07
申请号:CA771076D
Applicant: BASF AG
Inventor: ROSENKRANZ MAGNUS , POMMER HORST , HANTGE HARTMUT , STILZ WALTER
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公开(公告)号:GB1045443A
公开(公告)日:1966-10-12
申请号:GB4392064
申请日:1964-10-28
Applicant: BASF AG
Inventor: POMMER HORST , STILZ WALTER , HANTGE HARTMUT , ROSENKRANZ MAGNUS
Abstract: Synthetic linear polyester or polyamide shaped articles e.g fibres and films, are brightened by treating them from aqueous liquors or by means of print pastes with an aqueous dispersion of one or more of p-bis styrylbenzene having the formula (I) derivatives thereof which bear substituents on the benzene rings A, B1 and B2 and which are soluble in water to the extent of less than 1% by weight at 25 DEG C. and then fixing the compounds on the shaped articles at a temperature of 90 DEG -225 DEG C. The substituents on the benzene rings A1, B1 and B2 may be chlorine or bromine atoms or cyano, alkyl, alkoxy, alkyloyloxy, carbalkoxy, alkyl-carbamoyl or dialkylcarbamoyl groups, the alkyl radicals preferably containing up to four carbon atoms. Provided the compounds remain soluble in water to the extent of less than 1% by weight at 25 DEG C. hydroxyl, hydroxyalkyl, amino, alkylamino, carbamoyl and sulphonamide groups may also be substituents. The optical brightening agent may be p applied by the thermosol method on a padding machine as an aqueous dispersion which may contain thickeners, the treatment with the aqueous dispersion being followed by drying and a hot air treatment at 120 DEG -220 DEG C. in the case of polyamide materials and at 120 DEG -200 DEG C. in the case of polyester materials, or a treatment with superheated steam at 100 DEG -140 DEG C. Alternatively a high-temperature exhaustion method in which the material is maintained in the aqueous dispersion in a dyeing machine at a temperature above 100 DEG C. for 30-60 minutes and then dried at 90 DEG -225 DEG C. or an exhaustion method in which the material is introduced into the treatment liquor at 60 DEG -70 DEG C. and the temperature raised to 95 DEG -100 DEG C. for 30-60 minutes may be utilized. The aqueous dispersions may also contain dispersing agents, e.g. soaps, sulphite cellulose waste liquor, polyglycol ethers of fatty alcohols or fatty amines or condensation products of naphthalenesulphonic acids, substituted napthhalenesulphonic acids and formaldehyde, and in the case of polyester materials a carrier, e.g. dichlorobenzene, trichlorobenzene, o-phenylphenol, p-phenylphenol, benzoic acid, the p-chlorophenyl monoether of glycol and esters of benzoic acid. A disperse dye may be included in print pastes. The brightening may be effected in conjunction with chemical bleaching with sodium chlorite.
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