Polycarboxylic acid dye with low polymerization degree

Patent metadata

Field	Value
Publication number	US-9040634-B2
Application number	US-201113700092-A
Country	US
Kind code	B2
Filing date	May 23, 2011
Priority date	May 25, 2010
Publication date	May 26, 2015
Grant date	May 26, 2015

Abstract

The present invention provides a polycarboxylic acid dye with low polymerization degree, which is formed by using a macromolecule skeleton of polymaleic acid linked to an azo chromophore, an azo-metal complexation chromophore or an anthraquinone chromophore via a bridge group of amide or ester bond. The dye is useful for dyeing and printing leather, protein fiber, cellulose fiber and synthetic fiber.

First claim

The invention claimed is:

1. A polycarboxylic acid dye, wherein the dye is a polymerized polycarboxylic acid, or salt or ester thereof having a macromolecule skeleton of polymaleic acid, or salt or ester thereof linked to a chromophore via a bridge group of amide or ester bond, having a structural formula of:

in formula (1), the structural component A consists of the following three monomer units which are linked randomly, block or alternately in arbitrary sequence, present with respective numbers of n 1 , n 2 and n 3 :

wherein each of the structural component A can independently have same or different n 1 , same or different n 2 and/or same or different n 3 ,
wherein,
M is H, Na, K or a quaternary ammonium positive ion of formula 1-1:

in formula 1-1, r 1 , r 2 , r 3 and r 4 are hydrogen, a C 1 -C 12 linear alkyl, or a C 1 -C 12 linear alkenyl, wherein the r 1 , r 2 , r 3 and r 4 can be same or different;
n 1 =1-100; n 2 =0-100; n 3 =1-100; and n=an integer of 1-300;
X=O or NH, linked to a chromophore;
D is (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25) or (26) having the following structures:

in formula (2): R 1 is H or Cl; R 2 is H, Cl, CN, SO 3 Na, SO 2 NHR, SO 2 CH 2 CH 2 Y 1 or SO 2 NHCH 2 CH 2 Y 1 ; R 3 is H, Cl, CN, CONHR or COOR; R 4 is H, CH 3 , CN, COOR or C 6 H 5 ; R 5 is H, Cl, NHR, CN, SO 3 Na, SO 2 NHR, CONHR, COOR, NHCOR,

 Y 1 is Cl, OSO 3 X or N(CH 3 )CH 2 CH 2 SO 3 X; Y 2 is Cl, F, OR, NHCH 2 SO 3 X, N(R) 2 , N(CH 2 OH) 2 , N(C 2 H 4 OH) 2

 Y 3 is Cl, F, OR, NHCH 2 SO 3 X, N(R) 2 , N(CH 2 OH) 2 , N(C 2 H 4 OH) 2 ,

 Q is Cl or CH 3 ; R 6 is H, Cl, CN, NO 2 , SO 2 NHR, CONHR or COOR; R is H, or a linear, saturated alkyl of C p H 2p+1 , wherein: p is an integer with the proviso of 1≦p≦18; and Xis H, Na or K;

in formula (3): R 1 is H, OCH 3 or OCH 2 CH 3 ; R 2 is CH 3 , CH 2 CH 3 , CH 2 CH 2 OH, CH 2 CH 2 OCH 3 , CH 2 CH 2 Cl, CH 2 CH 2 CN or CH 2 CH 2 OCOCH 3 ; R 3 is CH 3 , CH 2 CH 3 , CH 2 CH 2 OH, CH 2 CH 2 OCH 3 , CH 2 CH 2 Cl, CH 2 CH 2 CN or CH 2 CH 2 OCOCH 3 ; R 4 is H, NHCOCH 3 , NHCOC 2 H 5 ,

 NHCOCY 4 ═CHY 5 or NHCOCHY 4 CH 2 Y 6; Y 1 is Cl, OSO 3 X or N(CH 3 )CH 2 CH 2 SO 3 X; Y 2 is Cl or F; Y 3 is Cl, F, OR, NHCH 2 SO 3 X, N(R) 2 , N(CH 2 OH) 2 , N(C 2 H 4 OH) 2 ,

 Y 4 is H or Br; Y 5 is H, Cl or Br; Y 6 is Br or OSO 3 X; Q is Cl or CH 3 ; R 5 is H, Cl, Br, CN, NO 2 , SO 3 Na, SO 2 NHR, CONHR or COOR; R 6 is H, Cl, Br, CN, NO 2 , CH 3 , OCH 3 , OC 2 H 5 , CONH 2 , COOCH 3 or COOC 2 H 5 ; R is H, or a linear, saturated alkyl of C p H 2p+1 , wherein: p is an integer with the proviso of 1≦p≦18; and Xis H, Na or K;

in formula (4): R 1 is H, OCH 3 or OCH 2 CH 3 ; R 2 is OH, OCH 3 , Cl, CN or OCOCH 3 ; R 3 is H, NHCOCH 3 , NHCOC 2 H 5 ,

NHCOCY 4 ═CHY 5 or NHCOCHY 4 CH 2 Y 6 ; R 4 is H, Cl, Br, CN, NO 2 , SO 3 Na, SO 2 NHR, CONHR or COOR; R 5 is H, Cl, Br, CN, NO 2 , SO 2 NHR, CONHR, SO 2 CH 2 CH 2 Y 1 , SO 2 NHCH 2 CH 2 Y 1 ,

 NHCOCY 4 ═CHY 5 or NHCOCHY 4 CH 2 Y 6; Y 1 is Cl, OSO 3 X or N(CH 3 )CH 2 CH 2 SO 3 X; Y 2 is Cl or F; Y 3 is Cl, F, OR, NHCH 2 SO 3 X, N(R) 2 , N(CH 2 OH) 2 , N(C 2 H 4 OH) 2 ,

 Y 4 is H or Br; Y 5 is H, Cl or Br; Y 6 is Br or OSO 3 X; Q is Cl or CH 3 ; R 6 is H, Cl, Br, CN, NO 2 , CH 3 , OCH 3 , OC 2 H 5 , CONH 2 , COOCH 3 or COOC 2 H 5 ; R is H, or a linear, saturated alkyl of C p H 2p+1 , wherein: p is an integer with the proviso of 1≦p≦18; and X is H, Na or K;

in formula (5): R 1 is H, OCH 3 or OCH 2 CH 3 ; R 2 is H, OH, OCH 3 , Cl, CN or OCOCH 3 ; R 3 is H, OH, OCH 3 , Cl, CN or OCOCH 3 ; R 4 is H, Cl, Br, CN, NO 2 , SO 3 Na, SO 2 NHR, CONHR or COOR; R 5 is H, Cl, Br, CN, NO 2 , SO 2 NHR, CONHR, SO 2 CH 2 CH 2 Y 1 , SO 2 NHCH 2 CH 2 Y 1 ,

 NHCOCY 4 ═CHY 5 or NHCOCHY 4 CH 2 Y 6 ; Y 1 is Cl, OSO 3 X or N(CH 3 )CH 2 CH 2 SO 3 X; Y 2 is Cl or F; Y 3 is Cl, F, OR, NHCH 2 SO 3 X, N(R) 2 , N(CH 2 OH) 2 , N(C 2 H 4 OH) 2 ,

 Y 4 is H or Br; Y 5 is H, Cl or Br; Y 6 is Br or OSO 3 X; Q is Cl or CH 3 ; R 6 is H, Cl, Br, CN, NO 2 , CH 3 , OCH 3 , OC 2 H 5 , CONH 2 , COOCH 3 or COOC 2 H 5 ; R is H, or a linear, saturated alkyl of C p H 2p+1 , wherein: p is an integer with the proviso of 1≦p≦18; and X is H, Na or K;

in formula (6): R 1 is H, OH or NH 2 ; R 2 is H, SO 3 Na or SO 2 NHR; R 3 is H, Cl, CN, SO 2 NHR, CONHR, COOR, NHR, NHCOR, SO 2 CH 2 CH 2 Y 1 , SO 2 NHCH 2 CH 2 Y 1 ,

 NHCOCY 4 ═CHY 5 or NHCOCHY 4 CH 2 Y 6 ; Y 1 is Cl, OSO 3 X or N(CH 3 )CH 2 CH 2 SO 3 X; Y 2 is Cl or F; Y 3 is Cl, F, OR, NHCH 2 SO 3 X, N(R) 2 , N(CH 2 OH) 2 , N(C 2 H 4 OH) 2 ,

Y 4 is H or Br; Y 5 is H, Cl or Br; Y 6 is Br or OSO 3 X; Q is Cl or CH 3 ; R 4 is H, SO 3 Na, SO 2 NHR, NHR or NHCOR; R 5 is H, SO 2 NHR, NHR or NHCOR; R 6 is H, Cl, NHR, CN, SO 3 Na, SO 2 NHR, CONHR, COOR or NHCOR; R 7 is H, Cl, CH 3 , OCH 3 , OC 2 H 5 , OH, CN, CONH 2 , COOCH 3 or COOC 2 H 5 ; R is H, or a linear, saturated alkyl of C p H 2p + 1 , wherein: p is an integer with the proviso of 1≦p≦18; and X is H, Na or K;

in formula (7): R 1 is H, OCH 3 or NHR; R 2 is H, SO 3 Na or SO 2 NHR; R 3 is H, Cl, CN, SO 3 Na, SO 2 NHR, CONHR, COOR, NHR or NHCOR; R 4 is H, SO 2 NHR, NHR or NHCOR; R 5 is H, SO 3 Na, SO 2 NHR, NHR, CONHR, COOR, NHCOR, SO 2 CH 2 CH 2 Y 1 , SO 2 NHCH 2 CH 2 Y 1 ,

 NHCOCY 4 ═CHY 5 or NHCOCHY 4 CH 2 Y 6; Y i is Cl, OSO 3 X or N(CH 3 )CH 2 CH 2 SO 3 X; Y 2

Assignees

• Zhang Shufen
• Tang Bingtao
• Ma Wei
• Univ Dalian Tech

Inventors

• Zhang Shufen
• Tang Bingtao
• Ma Wei

Classifications

• C09B1/22

  Dyes with unsubstituted amino groups · CPC title

• C09B69/109

  containing other specific dyes · CPC title

• C09B29/3604

  containing only a nitrogen as heteroatom · CPC title

• C09B69/106

  containing an azo dye · CPC title

• C08L37/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (of cyclic esters of polyfunctional acids C08L31/00; of cyclic anhydrides of unsaturated acids C08L35/00); Compositions of derivatives of such polymers · CPC title