CN110655609B - Textile dye fixing agent and application thereof - Google Patents
Textile dye fixing agent and application thereof Download PDFInfo
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- CN110655609B CN110655609B CN201910360302.2A CN201910360302A CN110655609B CN 110655609 B CN110655609 B CN 110655609B CN 201910360302 A CN201910360302 A CN 201910360302A CN 110655609 B CN110655609 B CN 110655609B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
Abstract
The invention provides a textile dye fixing agent and application thereof, belongs to the technical field of textile printing and dyeing auxiliaries, and particularly relates to a polymer which comprises a mol of at least one copolymerization unit shown as a formula (I), b mol of at least one copolymerization unit shown as a formula (II) and c mol of at least one copolymerization unit shown as a formula (III):
Description
Technical Field
The invention belongs to the technical field of textile printing and dyeing auxiliaries, and particularly relates to a textile dye fixing agent and application thereof.
Background
The cotton fabric is popular with consumers due to wide moisture absorption and air permeability, and the quality of the cotton fabric is more and more adapted to the increasingly improved wearing requirements of people through continuous development, wherein the mercerized cotton fabric is one of the products which are well received by the consumers, and the mercerized cotton fabric is comfortable to wear, has silky luster, stable, stiff and smooth in size and good in wrinkle resistance, and is widely applied to products such as T-shirts, moisture absorption and sweat releasing fabrics, high-grade shirts and the like. The conventional mercerizing process of the cotton knitted fabric is carried out before dyeing, but in subsequent dyeing and post-finishing processing, the mercerizing effect of the cotton knitted fabric is obviously influenced under the long-time repeated physical friction extrusion and chemical action, in order to keep the excellent performance of the cotton knitted fabric endowed with mercerizing and improve the product quality, a processing process route of dyeing firstly and then mercerizing is adopted for the cotton knitted fabric, but the processing method of dyeing firstly and then mercerizing enables the dyed fabric to be subjected to mercerizing concentrated alkali (NaOH 200-280 g/L), and the reactive dye is further hydrolyzed to cause flooding, so that the color fastness is seriously reduced, and the color fixing treatment needs a color fixing agent with excellent resistance, especially alkali resistance, so as to ensure the improvement of the fabric quality.
Disclosure of Invention
The invention aims to provide a textile dye fixing agent and application thereof, wherein the textile dye fixing agent is a polymer, the preparation method is simple, the reaction is mild, the phenomena of implosion, gelation and the like are avoided, a new branched structure with silicon carbon chains, nitrogen carbon chains and particularly silicon oxygen chains is introduced, sulfydryl is further introduced and condensed into disulfide bonds, the crosslinking density of the fixing agent is further increased, and the fastness of wear resistance, water bubble resistance and the like is greatly improved.
The technical scheme adopted by the invention for realizing the purpose is as follows:
[1] a textile dye fixing agent is a polymer which comprises a mol of at least one copolymerization unit shown as a formula (I), b mol of at least one copolymerization unit shown as a formula (II) and c mol of at least one copolymerization unit shown as a formula (III):
in the formula, the R1、R2、R5、R6、R7、R11、R13Each independently selected from hydrogen, halogen atom, C1-6Alkyl radical, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl group, C1-6Aralkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6Alkyl group, preferably halogen atom, C1-6Alkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group;
the R is4、R12、R14Each independently selected from C1-8Mercaptoalkyl, preferably C1-4A mercaptoalkyl group;
the R is9、R10Each independently selected from C1-6Alkyl group, halogen atom, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or C1-6Aralkyl, preferably C1-6Alkyl, halogen atom, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or C1-6Aralkyl group;
the R is3、R8Each independently selected from C1-6Alkylene radical, C1-6Hydroxyalkylene group, C1-6Carboxyalkylene group, C1-6Alkoxyalkylene group, C6-10Arylene, -C (O) O-, -C (O) OC0-6Alkylene, -C (O) NH-or-C (O) NHC0-6Alkylene, preferably C1-6Alkylene, -C (O) O-, -C (O) OC0-6Alkylene, -C (O) NH-or-C (O) NHC0-6An alkylene group;
each of m, n is independently 0, 1, 2, 3 or 4, and 7> m + n >0, preferably each of m, n is independently 1, 2 or 3;
the above-mentioned
Represents a counter-ion, and is represented by,
can be the same or different and can be selected from halide ions or oxygen-containing acid groups, preferably from Cl-Or (1/2SO4)-More preferably Cl-。
The molar ratio of a to b to c is 1: 0.1-1.5: 0.05-2, the molar ratio of a to b to c is more preferably 1: 0.5-1: 1-2, and the molar ratio of a to b to c is most preferably 1:1: 1.5.
The weight average molecular weight of the textile dye fixing agent is 5000-300000 g/mol, the weight average molecular weight of the textile dye fixing agent is more preferably 10000-100000 g/mol, and the weight average molecular weight of the textile dye fixing agent is most preferably 30000-50000 g/mol.
The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymer of the present invention as a textile dye fixing agent is preferably not more than 3, more preferably not more than 2.5, on a molecular weight basis.
The polymer chain used as the textile dye fixing agent has more branched chains, better polarity and good rheological property, and can greatly improve the coating strength of the fixing agent on dye molecules when being used as the dye fixing agent; in addition, three copolymerization units of the polymer chain contain sulfydryl, two sulfydryl are changed into a disulfide bond through oxidative dehydration, the space crosslinking of the color fixing agent can be greatly increased, the coating and fixing effects of the color fixing agent on dye molecules are enhanced, the tolerance of the color fixing agent can be increased, the silicon carbon chain and the nitrogen carbon chain, particularly the silicon oxygen chain, which are rich in the polymer chain can enable the color-fixed fabric and/or clothes to obtain soft touch and hand feeling, the wear resistance and the water bubble resistance of the dyed fabric and/or clothes are excellent, and meanwhile, the soaping resistance, the perspiration resistance and the rubbing resistance are good, the fabric color is less, and the hand feeling is soft.
[2] A process for producing a textile dye fixative as described in item [1], comprising polymerizing a monomer represented by the following general formula (I ') (II ') (III ') in the presence of an initiator:
in the formula, the R1、R2、R5、R6、R7、R11、R13Each independently selected from hydrogen, halogen atom, C1-6Alkyl radical, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl group, C1-6Aralkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6Alkyl group, preferably halogen atom, C1-6Alkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group;
the R is4、R12、R14Each independently selected from C1-8Mercaptoalkyl, preferably C1-4A mercaptoalkyl group;
the R is9、R10Each independently selected from C1-6Alkyl group, halogen atom, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or C1-6Aralkyl, preferably C1-6Alkyl, halogen atom, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or C1-6Aralkyl group;
the R is3、R8Each independently selected from C1-6Alkylene radical, C1-6Hydroxyalkylene group, C1-6Carboxyalkylene group, C1-6Alkoxyalkylene group, C6-10Arylene, -C (O) O-, -C (O) OC0-6Alkylene, -C (O) NH-or-C (O) NHC0-6Alkylene, preferably C1-6Alkylene, -C (O) O-, -C (O) OC0-6Alkylene, -C (O) NH-or-C (O) NHC0-6An alkylene group;
each of m, n is independently 0, 1, 2, 3 or 4, and 7> m + n >0, preferably each of m, n is independently 1, 2 or 3;
the above-mentioned
Represents a counter-ion, and is represented by,
can be the same or different and can be selected from halide ions or oxygen-containing acid groups, preferably from Cl-Or (1/2SO4)-More preferably Cl-。
The polymer serving as the textile dye fixing agent specifically comprises a mole of at least one copolymerization unit shown as a formula (I), b mole of at least one copolymerization unit shown as a formula (II) and c mole of at least one copolymerization unit shown as a formula (III), wherein the mole ratio of a to b to c is 1: 0.1-1.5: 0.05-2, the mole ratio of a to b to c is more preferably 1: 0.5-1: 1-2, and the mole ratio of a to b to c is most preferably 1:1: 1.5.
The weight average molecular weight of the polymer used as the textile dye fixing agent is 5000-300000 g/mol, more preferably 10000-100000 g/mol, and most preferably 30000-50000 g/mol.
The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymer of the present invention as a textile dye fixing agent is preferably not more than 3, more preferably not more than 2.5, on a molecular weight basis.
The polymer used as the textile dye fixing agent is prepared by copolymerizing a monomer mixture containing one or more monomers represented by the general formula (I '), one or more monomers represented by the general formula (II ') and one or more monomers represented by the general formula (III ') in the presence of a free radical initiator. (1) According to the invention, the trimerization double bond and the multi-polymerization double bond monomer are adopted, so that the crosslinking density of the prepared color fixing agent is greatly improved, and the fastness to water bubbles is obviously improved; (2) introducing silane monomers to ensure that the fabric after color fixation obtains soft hand feeling; (3) the hyperbranched polymer monomer participates in polymerization reaction, a new branched structure with a silicon carbon chain, a nitrogen carbon chain and particularly a silicon oxygen chain is introduced, so that the crosslinking density of the color fixing agent is further increased, the rheological property is good, the color-fixed fabric and/or clothes can obtain soft touch and hand feeling, and the wear resistance fastness and the water bubble resistance fastness of the dyed fabric and/or clothes are excellent; (4) the preparation method is simple and easy to operate, the polymerization reaction is mild, the occurrence of the phenomena of easy explosion, easy polymerization and easy gelation during the polymerization of the existing color fixing adhesive is avoided, the molecular weight range of the polymer generated by the reaction is narrow, and the molecular weight distribution index D is not more than 3, so that the polymer is uniform and stable in property. The color fixing agent prepared by the invention has good rheological property, excellent water-bubble fastness, good soaping fastness, perspiration fastness and rubbing fastness, small color change of fabrics and soft hand feeling.
When polymerized, the comonomer represented by the general formula (1') is polymerized to form polymerized units represented by the general formula (1):
in the formulae (I') and (I), the R1、R2Each independently selected from hydrogen, halogen atom, C1-6Alkyl radical, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl group, C1-6Aralkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group;
the R is4Independently selected from C1-8A mercaptoalkyl group;
the R is3Independently selected from C1-6Alkylene radical, C1-6Hydroxyalkylene group, C1-6Carboxyalkylene group, C1-6Alkoxyalkylene group, C6-10Arylene, -C (O) O-, -C (O) OC0-6Alkylene, -C (O) NH-or-C (O) NHC0-6An alkylene group;
the above-mentioned
Represents a counter-ion, and is represented by,
can be selected from halide or oxyacid groups, preferably from Cl-Or (1/2SO4)-More preferably Cl-。
When polymerized, the comonomer represented by the general formula (2') is polymerized to form a polymerized unit represented by the general formula (2):
in the formulae (II') and (II), the R5、R6、R7、R11Each independently selected from hydrogen, halogen atom, C1-6Alkyl radical, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl group, C1-6Aralkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group;
the R is12Independently selected from C1-8A mercaptoalkyl group;
the R is9、R10Each independently selected from C1-6Alkyl group, halogen atom, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or C1-6Aralkyl group;
the R is8Independently selected from C1-6Alkylene radical, C1-6Hydroxyalkylene group, C1-6Carboxyalkylene group, C1-6Alkoxyalkylene group, C6-10Arylene, -C (O) O-, -C (O) OC1-6Alkylene, -C (O) NH-or-C (O) NHC1-6An alkylene group;
each of m, n is independently 0, 1, 2, 3 or 4, and 7> m + n > 0;
the above-mentioned
Represents a counter-ion, and is represented by,
can be selected from halide or oxyacid groups, preferably from Cl-Or (1/2SO4)-More preferably Cl-。
When polymerized, the comonomer represented by the general formula (3') is polymerized to form a polymerized unit represented by the general formula (3):
in the formulae (III') and (III), the R13Independently selected from hydrogen, halogen atoms, C1-6Alkyl radical, C1-6Hydroxyalkyl radical, C1-6Carboxyalkyl, C1-6Alkoxyalkyl group, C1-6Aralkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group;
the R is14Independently selected from C1-8A mercaptoalkyl group.
The polymer serving as the textile dye fixing agent specifically comprises a mole of at least one copolymerization unit shown as a formula (I), b mole of at least one copolymerization unit shown as a formula (II) and c mole of at least one copolymerization unit shown as a formula (III), wherein the mole ratio of a to b to c is 1: 0.1-1.5: 0.05-2, the mole ratio of a to b to c is more preferably 1: 0.5-1: 1-2, and the mole ratio of a to b to c is most preferably 1:1: 1.5.
The weight average molecular weight of the polymer used as the textile dye fixing agent is 5000-300000 g/mol, more preferably 10000-100000 g/mol, and most preferably 30000-50000 g/mol.
The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymer of the present invention as a textile dye fixing agent is preferably not more than 3, more preferably not more than 2.5, on a molecular weight basis.
Based on the structure, the polymer serving as the textile dye fixing agent is a copolymer, and can be a random copolymer, an alternating copolymer, a graft copolymer or a block copolymer or a mixed structure containing at least two of random, alternating, graft and block.
Specifically, the method for preparing the textile dye fixing agent according to item 2 comprises the following steps:
a) preparing a monomer shown in a formula (I ') and a monomer shown in a formula (II') into an aqueous emulsion at 42-55 ℃ in the presence of an emulsifier;
b) adding a monomer shown in a formula (III') and an initiator at 62-75 ℃, and carrying out emulsion polymerization under inert gas;
c) and cooling, adjusting the pH value to 7-8, and keeping the temperature for 2-3 h to obtain the product.
In the summary and the preferred embodiment of the present invention, in the step a), the aqueous emulsion is preferably prepared by stirring at 42 to 55 ℃ for 5 to 30min, and more preferably at 45 to 50 ℃ for 15 to 25 min.
In the summary of the invention and the preferred embodiment, in the step a), the emulsifier is one of dodecyl dimethyl benzyl ammonium chloride, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, fatty amine polyoxyethylene ether or a combination thereof.
In the summary and preferred embodiment of the present invention, in the step a), the emulsifier is added in an amount of 0.01 to 1 wt% of the total weight of the polymerization unit.
In the summary and the preferred embodiment of the invention, in the step b), the addition amount of the initiator is 0.5-0.8 wt% of the total weight of the polymerized monomers based on the total weight of the monomers, and the addition is completed by dropwise adding for 1-3 h; the more preferable adding amount of the initiator is 0.7-0.8 wt% of the total weight of the polymerization monomers, and the adding mode is completed by dropwise adding for 2-3 h.
In the present disclosure and preferred embodiments, in the step b), the initiator is preferably a radical initiator, and the radical initiator preferably includes a thermal radical initiator, a photo radical initiator or a redox initiator, and most preferably a redox initiator.
In the present disclosure and preferred embodiments, the initiator in step b) may be an O-acyloxime compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, and an acylphosphine oxide compound. Specific examples include, but are not limited to, N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropan-1-one-2-imine, Irgacure OXE01(BASF), Irgacure OXE02(BASF), N-1919(ADEKA), 2 methyl-2-morpholinyl-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinylphenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one, Irgacure369(BASF), Irgacure907(BASF), Irgacure379(BASF), alpha-diethoxyacetophenone, benzildimethylketal, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylimidazole, 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (trialkoxyphenyl) biimidazole, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuryl-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furyl-2-yl) vinyl ] -1,3, 5-triazine, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
In the present disclosure and preferred embodiments, examples of the initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzoyl, methyl phenylglyoxylate, titanocene compounds, and the like.
In the summary and preferred embodiment of the present invention, in the step c), the temperature is reduced to 35 to 65 ℃ and kept for 2 to 3 hours, more preferably, the temperature is reduced to 50 to 60 ℃ and kept for 2.5 to 3 hours.
In the summary and preferred embodiment of the present invention, in the step c), the inert gas is nitrogen.
In the invention, in the method for preparing the polymer as the textile dye fixing agent, basically all monomers are polymerized into the polymer, and the molar ratio of the repeating units represented by the general formulas (I), (II) and (III) in the formed polymer is 1: 0.1-1.5: 0.05-2, more preferably 1: 0.5-1: 1-2, and most preferably 1:1: 1.5.
In the present disclosure and preferred embodiments, in the preparation method of the polymer as the textile dye fixing agent, substantially all monomers are polymerized into the polymer of the present invention, and in the formed polymer of the present invention, the weight average molecular weight of the polymer is 5000-300000 g/mol, more preferably 10000-100000 g/mol, and most preferably 30000-50000 g/mol.
In the present disclosure and preferred embodiments, in the process for preparing the polymer as a textile dye fixing agent, substantially all of the monomers are polymerized into the polymer of the present invention, and the resulting polymer of the present invention preferably has a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of not greater than 3, more preferably not greater than 2.5.
The preparation method of the polymer serving as the textile dye fixing agent is simple and easy to operate, the polymerization reaction is mild, the phenomena that the existing fixing agent is easy to explode, polymerize and gel when being polymerized are avoided, the molecular weight range of the polymer generated by the reaction is narrow, and the molecular weight distribution index D is not more than 3, so that the polymer is uniform and stable in property and can be used in the fields of dye adhesives, fixing agents and the like; the trimerization double bond and the multi-polymerization double bond monomer are adopted, so that the crosslinking density of the prepared color fixing agent is greatly improved, and the fastness to water bubbles is obviously improved; introducing silane monomers and introducing a new branched structure with silicon carbon chains, nitrogen carbon chains and particularly silicon oxygen chains, so that the crosslinking density of the color fixing agent is further increased, the rheological property is good, the color-fixed fabric and/or clothes can obtain soft touch and hand feeling, and the wear resistance fastness and the water bubble resistance fastness of the dyed fabric and/or clothes are excellent; the hyperbranched polymer monomer participates in polymerization reaction, sulfhydryl groups in a polymer chain are subjected to dehydration reaction under an alkaline condition to generate disulfide bonds, so that hyperbranched and space crosslinking effects of the polymer can be greatly enhanced, the crosslinking density of the polymer serving as a color fixing agent is improved, the wear fastness and the bubble fastness of fabrics dyed by the color fixing agent are improved, and meanwhile, the soaping fastness, the perspiration fastness and the rubbing fastness are good, the fabric color is reduced, and the hand feeling is soft.
[3] The present invention also provides the use of the polymer as a textile dye fixing agent as described in the item [1] and/or [2] for dye printing, wherein the polymer is used as a main component of the dye fixing agent.
The invention has the beneficial effects that:
1) the preparation method of the polymer used as the textile dye fixing agent is simple and easy to operate, the polymerization reaction is mild, and the phenomena of easy explosion, easy polymerization and easy gelation during the polymerization of the conventional fixing agent are avoided;
2) the molecular weight range of the polymer generated by the reaction is narrow, and the molecular weight distribution index D is not more than 3, so that the polymer is uniform and stable in property and can be used in the fields of dye adhesives, color fixing agents and the like;
3) the trimerization double bond and the multi-polymerization double bond monomer are adopted, so that the crosslinking density of the prepared color fixing agent is greatly improved, and the fastness to water bubbles is obviously improved; introducing silane monomers and introducing a new branched structure with silicon carbon chains, nitrogen carbon chains and particularly silicon oxygen chains, so that the crosslinking density of the color fixing agent is further increased, the rheological property is good, and the color-fixed fabric and/or clothes can obtain soft touch and hand feeling;
4) the hyperbranched polymer monomer participates in polymerization reaction, and sulfhydryl groups in a polymer chain undergo dehydration reaction under an alkaline condition to generate disulfide bonds, so that hyperbranched and space crosslinking effects of the polymer can be greatly enhanced, and the crosslinking density of the polymer serving as a color fixing agent is improved;
5) the wear resistance fastness and the water bubble fastness of the fabric dyed by the color fixing agent are improved, and meanwhile, the soaping fastness, the perspiration fastness and the rubbing fastness are good, the color change of the fabric is small, and the hand feeling is soft;
6) the textile dye fixing agent and the application thereof provided by the invention make up for the defects of the prior art, and are reasonable in design and convenient to operate.
Detailed Description
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
For the words "for example" and "such as" and grammatical equivalents thereof, the phrase "without limitation" should be understood to follow general usage unless explicitly stated otherwise. As used herein, the word "about" refers to variations due to experimental error. Unless expressly stated otherwise, all measurements described herein, whether or not explicitly used, are to be understood as being modified by the word "about". As used herein, the singular forms "a," "an," and "the" ("a," "an," and "the") include plural referents unless the context clearly dictates otherwise.
For the words "for example" and "such as" and grammatical equivalents thereof, the phrase "without limitation" should be understood to follow general usage unless explicitly stated otherwise. As used herein, the word "about" refers to variations due to experimental error. Unless expressly stated otherwise, all measurements described herein, whether or not explicitly used, are to be understood as being modified by the word "about". As used herein, the singular forms "a," "an," and "the" ("a," "an," and "the") include plural referents unless the context clearly dictates otherwise.
The compounds provided herein may also include all isotopes of atoms occurring in the intermediates or final compounds. Isotopes include those atoms having the same atomic number but different mass numbers. For example, isotopes of hydrogen include hydrogen, tritium, deuterium.
The term "compound" as used herein, is meant to include all stereoisomers, geometric isomers, tautomers and isotopes of the structures depicted. A compound identified herein by name or structure as one particular tautomeric form includes other tautomeric forms unless otherwise specified. All compounds, and pharmaceutically acceptable salts thereof, may contain other substances such as water and solvents (e.g., hydrates and solvates).
The term "C" as used hereinx-yAlkyl "refers to substituted or unsubstituted saturated hydrocarbon radicals, including chain-containingStraight and branched alkyl groups having from x to y carbon atoms. E.g. C1-6Alkyl is meant to have the full range of carbon numbers (i.e., 1 to 6 carbon atoms), as well as all subgroups (e.g., 1-6, 2-6, 1-5, 3-6, 2-5, 3-4, 1, 2, 3, 4, 5, and 6 carbon atoms).
The term "alkoxy" as used herein refers to a C having an oxygen attached thereto1-4Alkyl groups including methoxy, ethoxy, propoxy and tert-butoxy.
The term "C" as used hereinx-yAlkoxyalkyl "means C substituted by" alkoxyx-yAlkyl, as defined above. For example, the term "C1-6Alkoxyalkyl "means C substituted by alkoxy1-6Alkyl, thereby forming an ether.
The term "C" as used hereinx-yHydroxyalkyl "means C substituted with hydroxyx-yAlkyl, as defined above. For example, the term "C1-6Hydroxyalkyl "means C substituted by one hydroxy group1-6An alkyl group.
The term "C" as used hereinx-yCarboxyalkyl "means C substituted with carboxyx-yAlkyl, as defined above. For example, the term "C1-6Carboxyalkyl "means C substituted by one carboxy group1-6An alkyl group.
The term "C" as used hereinx-yMercaptoalkyl "refers to C substituted with a carbonyl groupx-yAlkyl, as defined above. For example, the term "C1-6Mercaptoalkyl "means C substituted by one mercapto group1-6An alkyl group.
The term "C" as used hereinx-yAlkylene "is derived from an alkyl group, as defined above, with one hydrogen atom of the alkyl group removed. For example, the term "C1-6Alkylene "means C with one hydrogen atom removed1-6An alkyl group. Also, the term "C" as used herein1-6Hydroxyalkylene group and C1-6Carboxyalkylene group and C1-6Alkoxyalkylene "is as defined above. For example, the term "C1-6Carboxyalkylene "means removal of oneC of hydrogen atoms1-6Carboxyalkyl, the remainder of which are not described in detail.
The term "C" as used hereinx-yArylene "is derived from aromatic hydrocarbons (aromatics) in which one hydrogen atom is removed from each of the two ring carbon atoms. For example, the term "C6-10Arylene "means C6-10One hydrogen atom of each of the two ring carbon atoms of the arene is removed, including but not limited to, as described by the following formula:
the term "radical initiator" used herein is not particularly limited as long as it is a compound which generates an active radical by the action of light or heat and can initiate polymerization, and a known polymerization initiator can be used.
Other features and advantages of the invention will be apparent from the following detailed description, and from the claims. The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The application and performance of the polymers prepared in the following examples as textile dye fixing agents on textiles were determined:
1) fabric: the red all-cotton knitted fabric is dyed by reactive dye, wherein the dye used for dyeing is C.I. solvent red 49, and the dyeing concentration is 5% o.w.f.;
2) the dye fixing agent comprises the following components in parts by weight: the amount of polymer used as textile dye fixing agent was 0.8% o.w.f., bath ratio 1: 25;
3) sample preparation: the red all-cotton knitted fabric process comprises the following steps: dipping color fixing liquid (0.8% o.w.f., pH value of working liquid is 5, bath ratio is 1:25, 40 ℃ and 30min) → dewatering → drying.
4) Textile performance determination standards:
and A, bubble fastness resistance: the method comprises the following steps of heating 1 g/L of fringed washing powder at a bath ratio of 1:50 to 90 ℃, putting a cloth sample treated by a color fixing agent into the cloth sample, oscillating the cloth sample in a dyeing oscillator for 5min, taking out the cloth sample, and measuring the color depth of a working solution according to a grey sample card for color change evaluation of GB/T250-2008 textile color fastness test;
b color fastness to soaping: measured according to GB/T3921-;
c color fastness to perspiration: measuring according to the color fastness to perspiration of GB/T3922 and 2013 textile color fastness test;
d color fastness to rubbing: the determination is carried out according to GB/T3920 and 2008 textile color fastness test rubbing color fastness;
e, color change: determining according to a grey sample card for evaluating color change in GB/T250 + 2008 textile color fastness test;
f, hand feeling: and (3) adopting a multi-person touch method, scoring a group of 5 persons, and taking the average score as an evaluation result, wherein the score of 5 is the best, and the score of 1 is the worst.
In each example, all the materials and fabrics were commercially available.
Example 1:
the embodiment provides a textile dye fixing agent, which is specifically a polymer comprising a mol of a copolymerization unit shown as a formula (I-1), b mol of a copolymerization unit shown as a formula (II-1) and c mol of a copolymerization unit shown as a formula (III-1):
in the formula, the R1、R2、R5、R6Are each hydrogen, R7is-CH2CH3，R11is-CH2CH2OH、R13is-C (O) OCH2CH3(ii) a The R is4is-CH2CH2SH，R12is-CH2SH，R14is-CH2CH2CH2SH; the R is9is-CH3，R10is-CH2CH2COOH; the R is3is-C (O) O-, R8is-C (O) NH-; both m and n are 1; the above-mentioned
Represent counter ions, all being Cl-。
The molar ratio of a to b to c is 1:1.5:2 on a molar basis; based on the weight-average molecular weight, the weight-average molecular weight of the textile dye fixing agent is 30000-50000 g/mol; the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymer of the present invention as a textile dye fixing agent was 2.2 on a molecular weight basis.
The polymer chain used as the textile dye fixing agent has more branched chains, better polarity and good rheological property, and can greatly improve the coating strength of the fixing agent on dye molecules when being used as the dye fixing agent; in addition, three copolymerization units of the polymer chain contain sulfydryl, two sulfydryl are changed into a disulfide bond through oxidative dehydration, the space crosslinking of the color fixing agent can be greatly increased, the coating and fixing effects of the color fixing agent on dye molecules are enhanced, the tolerance of the color fixing agent can be increased, the silicon carbon chain and the nitrogen carbon chain, particularly the silicon oxygen chain, which are rich in the polymer chain can enable the color-fixed fabric and/or clothes to obtain soft touch and hand feeling, the wear resistance and the water bubble resistance of the dyed fabric and/or clothes are excellent, and meanwhile, the soaping resistance, the perspiration resistance and the rubbing resistance are good, the fabric color is less, and the hand feeling is soft.
This example also provides a process for preparing the above dye fixative for textile dyes, comprising polymerizing a monomer represented by the following general formula (I ' -1) (II ' -1) (III ' -1) in the presence of an initiator:
in the formula, the R1、R2、R5、R6Are each hydrogen, R7is-CH2CH3，R11is-CH2CH2OH、R13is-C (O) OCH2CH3(ii) a The R is4is-CH2CH2SH，R12is-CH2SH，R14is-CH2CH2CH2SH; the R is9is-CH3，R10is-CH2CH2COOH; the R is3is-C (O) O-, R8is-C (O) NH-; both m and n are 1; the above-mentioned
Represent counter ions, all being Cl-。
The molar ratio of a to b to c is 1:1.5:2 on a molar basis; based on the weight-average molecular weight, the weight-average molecular weight of the textile dye fixing agent is 30000-50000 g/mol; the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymer of the present invention as a textile dye fixing agent was 2.2 on a molecular weight basis.
Specifically, the preparation method of the polymer as the textile dye fixing agent comprises the following steps:
a) preparing a monomer shown in a formula (I '-1) and a monomer shown in a formula (II' -1) into an aqueous emulsion at 45 ℃ in the presence of an emulsifier;
b) adding a monomer shown in a formula (III' -1) and an initiator at 65 ℃ and carrying out emulsion polymerization under inert gas;
c) cooling, adjusting pH to 7.2, and keeping the temperature for 3 h.
In the step a), the aqueous emulsion is prepared by stirring for 25min at 45 ℃;
in the step a), the emulsifier is octadecyl trimethyl ammonium chloride, and the addition amount of the emulsifier is 0.5 wt% of the total weight of the polymerization monomer;
in the step b), the addition amount of the initiator is 0.8 wt% of the total weight of the polymerization monomers based on the total weight of the monomers, and the addition mode is completed by dropwise adding for 3 h;
in step b), the initiator is 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
In the step c), cooling to 40 ℃ and preserving heat for 2 h;
in the step c), the inert gas is nitrogen.
The polymer used as the textile dye fixing agent is prepared by copolymerizing a monomer mixture containing one or more monomers represented by the general formula (I ' -1), one or more monomers represented by the general formula (II ' -1) and one or more monomers represented by the general formula (III ' -1) in the presence of a free radical initiator. (1) According to the invention, the trimerization double bond and the multi-polymerization double bond monomer are adopted, so that the crosslinking density of the prepared color fixing agent is greatly improved, and the fastness to water bubbles is obviously improved; (2) introducing silane monomers to ensure that the fabric after color fixation obtains soft hand feeling; (3) the hyperbranched polymer monomer participates in polymerization reaction, a new branched structure with a silicon carbon chain, a nitrogen carbon chain and particularly a silicon oxygen chain is introduced, so that the crosslinking density of the color fixing agent is further increased, the rheological property is good, the color-fixed fabric and/or clothes can obtain soft touch and hand feeling, and the wear resistance fastness and the water bubble resistance fastness of the dyed fabric and/or clothes are excellent; (4) the preparation method is simple and easy to operate, the polymerization reaction is mild, the occurrence of the phenomena of easy explosion, easy polymerization and easy gelation during the polymerization of the existing color fixing adhesive is avoided, the molecular weight range of the polymer generated by the reaction is narrow, and the molecular weight distribution index D is not more than 3, so that the polymer is uniform and stable in property. The color fixing agent prepared by the invention has good rheological property, excellent water-bubble fastness, good soaping fastness, perspiration fastness and rubbing fastness, small color change of fabrics and soft hand feeling.
When polymerized, the comonomer represented by the general formula (I' -1) is polymerized to form a polymerized unit represented by the general formula (I-1):
the comonomer represented by the general formula (II' -1) is polymerized to form a polymerized unit represented by the general formula (II-1):
the comonomer represented by the general formula (III' -1) is polymerized to form a polymerized unit represented by the general formula (III-1):
example 2:
the present embodiment provides the item [1 ]: a textile dye fixing agent, which is a polymer comprising a moles of copolymerized units represented by the following formula (I-2), b moles of copolymerized units represented by the following formula (II-2), and c moles of copolymerized units represented by the following formula (III-2):
the present embodiment also provides the item [2 ]: the preparation method of the polymer for the textile dye fixing agent according to item [1], which comprises polymerizing monomers represented by the following formulas (I '-2), (II' -2) and (III '-2) in the presence of an initiator, wherein the copolymerized unit represented by the formula (I-2) in item [1] is obtained from the following formula (I' -2), the copolymerized unit represented by the formula (II-2) in item [1] is obtained from the following formula (II '-2), and the copolymerized unit represented by the formula (III-2) in item [1] is obtained from the following formula (III' -2).
The method specifically comprises the following steps:
a) preparing a monomer shown in a formula (I '-2) and a monomer shown in a formula (II' -2) into an aqueous emulsion at 52 ℃ in the presence of an emulsifier;
b) adding a monomer shown in the formula (III' -2) and an initiator at 72 ℃ and carrying out emulsion polymerization under inert gas;
c) cooling, adjusting pH to 7.6, and keeping the temperature for 2.5 h.
In the preferred embodiment, the aqueous emulsion is prepared in step a) by stirring at 52 ℃ for 20 min.
In this preferred embodiment, in the step a), the emulsifier is dodecyl dimethyl benzyl ammonium chloride.
In the preferred embodiment, the emulsifier is added in an amount of 0.6 wt% based on the total weight of the polymerization mixture in step a).
In the preferred embodiment, the initiator is added in the step b) in an amount of 0.6 wt% based on the total weight of the monomers, and the addition is completed in a dropwise manner within 2.5 h.
In this preferred embodiment, in the step b), the initiator is 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbenzimidazole.
In the preferred embodiment, in the step c), the temperature is reduced to 60 ℃ and kept for 2 h.
In the preferred embodiment, in the step c), the inert gas is nitrogen.
In the preferred embodiment, in the preparation method of the polymer as the textile dye fixing agent, basically all monomers are polymerized into the polymer of the invention, and the molar ratio of the repeating units represented by the general formulas (I), (II) and (III) in the formed polymer of the invention is 1:1: 1.5.
In the preferred embodiment, in the preparation method of the polymer used as the textile dye fixing agent, basically all monomers are polymerized into the polymer, and in the formed polymer, the weight average molecular weight of the polymer is 35000-50000 g/mol.
In the preferred embodiment, in the process for preparing the polymer as a textile dye fixing agent, substantially all of the monomers are polymerized into the polymer of the present invention, and the resulting polymer of the present invention has a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of 2.3.
The preparation method of the polymer serving as the textile dye fixing agent is simple and easy to operate, the polymerization reaction is mild, the phenomena that the existing fixing agent is easy to explode, polymerize and gel when being polymerized are avoided, the molecular weight range of the polymer generated by the reaction is narrow, and the molecular weight distribution index D is not more than 3, so that the polymer is uniform and stable in property and can be used in the fields of dye adhesives, fixing agents and the like; the trimerization double bond and the multi-polymerization double bond monomer are adopted, so that the crosslinking density of the prepared color fixing agent is greatly improved, and the fastness to water bubbles is obviously improved; introducing silane monomers and introducing a new branched structure with silicon carbon chains, nitrogen carbon chains and particularly silicon oxygen chains, so that the crosslinking density of the color fixing agent is further increased, the rheological property is good, the color-fixed fabric and/or clothes can obtain soft touch and hand feeling, and the wear resistance fastness and the water bubble resistance fastness of the dyed fabric and/or clothes are excellent; the hyperbranched polymer monomer participates in polymerization reaction, sulfhydryl groups in a polymer chain are subjected to dehydration reaction under an alkaline condition to generate disulfide bonds, so that hyperbranched and space crosslinking effects of the polymer can be greatly enhanced, the crosslinking density of the polymer serving as a color fixing agent is improved, the wear fastness and the bubble fastness of fabrics dyed by the color fixing agent are improved, and meanwhile, the soaping fastness, the perspiration fastness and the rubbing fastness are good, the fabric color is reduced, and the hand feeling is soft.
The invention also provides the item [3 ]: use of the polymer as a textile dye fixing agent according to item [1] and/or [2] in dye printing, wherein the polymer is used as a main component of the dye fixing agent.
Example 3:
example 3 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -3), (II '-3) and (III' -3), respectively, and thus its copolymerized units are the corresponding copolymerized units formed after opening the carbon-carbon double bond of the corresponding monomers.
Example 4:
example 4 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -4), (II '-4) and (III' -4), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening of the carbon-carbon double bond of the corresponding monomers.
Example 5:
example 5 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -5), (II '-5) and (III' -5), respectively, and thus its copolymerized units are the corresponding copolymerized units formed after opening the carbon-carbon double bond of the corresponding monomers.
Example 6:
example 6 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -6), (II '-6) and (III' -6), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening of the carbon-carbon double bond of the corresponding monomers.
Example 7:
example 7 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -7), (II '-7) and (III' -7), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening of the carbon-carbon double bond of the corresponding monomers.
Example 8:
example 8 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -8), (II '-8) and (III' -8), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bond of the corresponding monomers.
Example 9:
example 9 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -9), (II '-9) and (III' -9), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bond of the corresponding monomers.
Example 10:
example 10 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -10), (II '-10) and (III' -10), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bonds of the corresponding monomers.
Example 11:
example 11 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -11), (II '-11) and (III' -11), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bonds of the corresponding monomers.
Example 12:
example 12 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -12), (II '-12) and (III' -12), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bonds of the corresponding monomers.
Example 13:
example 13 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -13), (II '-13) and (III' -13), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bond of the corresponding monomers.
Example 14:
example 14 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -14), (II '-14) and (III' -14), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening the carbon-carbon double bonds of the corresponding monomers.
Example 15:
example 15 is substantially the same as example 2 except that (I '-2), (II' -2) and (III '-2) in example 2 are replaced with the following (I' -15), (II '-15) and (III' -15), respectively, and thus the copolymerized units thereof are the corresponding copolymerized units formed after opening of the carbon-carbon double bond of the corresponding monomers.
Comparative example V16:
comparative example V16 is substantially the same as example 2 except that the comonomers include only (I '-16), (II' -16) below, and thus the copolymerized units are those formed by opening the carbon-carbon double bonds of the corresponding monomers.
Comparative example V17:
comparative example V17 is substantially the same as example 2 except that the comonomers include only the following (I '-17), (II' -17), and thus the copolymerized units are the corresponding copolymerized units formed after opening the carbon-carbon double bonds of the corresponding monomers.
Comparative example V18:
comparative example V18 is essentially the same as example 2 except that the comonomers include only the following (I '-18) and (III' -18), and thus the copolymerized units are those formed after opening the carbon-carbon double bonds of the corresponding monomers.
Comparative example V19:
comparative example V19 is essentially the same as example 2 except that the comonomers include only the following (I '-19) and (III' -19), and thus the copolymerized units are those formed after opening the carbon-carbon double bonds of the corresponding monomers.
Comparative example V20:
comparative example V20 is essentially the same as example 2 except that the comonomers include only the following (II ' -20) and (III ' -20) in place of (I ' -2), (II ' -2) and (III ' -2) in example 2, and thus the copolymerized units are those formed after opening the carbon-carbon double bonds of the corresponding monomers.
Comparative example V21:
comparative example V21 is essentially the same as example 2 except that the comonomers include only the following (II '-21) and (III' -21) whose copolymerized units are the corresponding copolymerized units formed after opening the carbon-carbon double bonds of the corresponding monomers.
The results of the measurements of the application and performance of the polymers prepared in examples 1-15 and comparative examples V16-V21 on textiles as dye fixatives were shown in Table 1, with no added fixing agent as a blank. As can be seen from Table 1, the polymer used as a textile dye fixing agent in the invention can make the fixed fabric obtain soft touch and hand feeling, and the fabric has excellent wear fastness and bubble fastness, good soaping fastness, perspiration fastness and rubbing fastness, small fabric color change and soft hand feeling.
TABLE 1 Effect of application
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (9)
1. The textile dye fixing agent is characterized by specifically being a copolymer containing a copolymerization unit shown as a formula (I), a copolymerization unit shown as a formula (II) and a copolymerization unit shown as a formula (III), wherein the molar ratio of the copolymerization units (I), (II) and (III) is a: b: c, and the copolymerization units (I), (II) and (III) are as follows:
wherein the molar ratio of a to b to c is 1: 0.1-1.5: 0.05-2; the R is1、R2、R5、R6、R7、R11、R13Each independently selected from hydrogen, halogen atom, C1-6Alkyl, hydroxy substituted C1-6Alkyl, carboxy substituted C1-6Alkyl, alkoxy substituted C1-6Alkyl, aryl substituted C1-6Alkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group; the R is4、R12、R14Each independently selected from mercapto-substituted C1-8An alkyl group; the R is9、R10Are each independently selected from C1-6Alkyl, halogen atom, hydroxy-substituted C1-6Alkyl, carboxy substituted C1-6Alkyl, alkoxy substituted C1-6Alkyl, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or aryl substituted C1-6An alkyl group; the R is3、R8Are each independently selected from C1-6Alkylene, hydroxy-substituted C1-6Alkylene, carboxyl substituted C1-6Alkylene, alkoxy-substituted C1-6Alkylene radical, C6-10Arylene, -C (O) OC0-6Alkylene or-C (O) NHC0-6An alkylene group; m and n are each independently 0, 1, 2, 3 or 4, and 7>m+n>0; the above-mentioned
Represents a counter-ion, and is represented by,
can be the same or different and is selected from halide ions or oxyacid groups.
2. The textile dye fixing agent according to claim 1, wherein R is1、R2、R5、R6、R7、R11、R13Each independently selected from halogen atom, C1-6Alkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group; the R is4、R12、R14Each independently selected from mercapto-substituted C1-4An alkyl group; the R is9、R10Are each independently selected from C1-6Alkyl, halogen atom, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or aryl substituted C1-6An alkyl group; the R is3、R8Are each independently selected from C1-6Alkylene, -C (O) OC0-6Alkylene or-C (O) NHC0-6An alkylene group; m and n are each independently 1, 2 or 3; the above-mentioned
Represents a counter-ion, and is represented by,
may be the same or different and are selected from Cl-Or (1/2 SO)4)-。
3. The textile dye fixing agent according to claim 1 or 2, wherein the weight average molecular weight of the copolymer is 5000-300000 g/mol; the copolymer has a molecular weight distribution of not more than 3 in terms of molecular weight distribution.
4. A textile dye fixative as claimed in claim 1 or claim 2 wherein the copolymer is at least one of a random copolymer, an alternating copolymer, a graft copolymer or a block copolymer.
5. A process for the preparation of a textile dye fixative as defined in claim 1 comprising polymerizing monomers of the following formula (I ') (II ') (III ') in the presence of an initiator:
in the formula, the R1、R2、R5、R6、R7、R11、R13Each independently selected from hydrogen, halogen atom, C1-6Alkyl, hydroxy substituted C1-6Alkyl, carboxy substituted C1-6Alkyl, alkoxy substituted C1-6Alkyl, aryl substituted C1-6Alkyl, -C (O) OC1-6Alkyl or-C (O) NHC1-6An alkyl group; the R is4、R12、R14Each independently selected from mercapto-substituted C1-8An alkyl group; the R is9、R10Are each independently selected from C1-6Alkyl, halogen atom, hydroxy-substituted C1-6Alkyl, carboxy substituted C1-6Alkyl, alkoxy substituted C1-6Alkyl, -C (O) OC1-6Alkyl, -C (O) NHC1-6Alkyl or aryl substituted C1-6An alkyl group; the R is3、R8Are each independently selected from C1-6Alkylene, hydroxy-substituted C1-6Alkylene, carboxyl substituted C1-6Alkylene, alkoxy-substituted C1-6Alkylene radical, C6-10Arylene, -C (O) OC0-6Alkylene or-C (O) NHC0-6An alkylene group; m and n are each independently 0, 1, 2, 3 or 4, and 7>m+n>0; the above-mentioned
Represents a counter-ion, and is represented by,
may be the same or different and are selected from the group consisting of halide ionsOr an oxygen acid radical.
6. The method of preparing a textile dye fixing agent as defined in claim 5, wherein the method of preparation comprises the steps of:
a) preparing a monomer shown in a formula (I ') and a monomer shown in a formula (II') into an aqueous emulsion at 42-55 ℃ in the presence of an emulsifier;
b) adding a monomer shown in a formula (III') and an initiator at 62-75 ℃, and carrying out emulsion polymerization under inert gas;
c) and cooling, adjusting the pH value to 7-8, and keeping the temperature for 2-3 h to obtain the product.
7. The method for preparing the textile dye fixing agent according to claim 6, wherein in the step a), the emulsifier is one of dodecyl dimethyl benzyl ammonium chloride, octadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, fatty amine polyoxyethylene ether or a combination thereof.
8. The preparation method of the textile dye fixing agent according to claim 5 or 6, wherein the addition amount of the initiator is 0.5-0.8 wt% of the total weight of the polymerization monomers based on the total weight of the monomers, and the addition is completed by dropwise addition for 1-3 h.
9. The method for preparing a textile dye fixing agent according to claim 5 or 6, characterized in that the initiator is a free radical initiator.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3472820A (en) * | 1964-06-19 | 1969-10-14 | Oreal | Polymercapto condensation polymers derived from maleic anhydride copolymers and aminothiols and their application for cosmetic purposes |
| US3549602A (en) * | 1964-06-19 | 1970-12-22 | Oreal | Polysulfhydryl polymers |
| US3576592A (en) * | 1965-02-23 | 1971-04-27 | Oreal | Process for permanently pressing textile articles made of keratinic fibers |
| JPH05321171A (en) * | 1992-05-19 | 1993-12-07 | Dai Ichi Kogyo Seiyaku Co Ltd | Fastness improver |
| JP2008115474A (en) * | 2006-10-31 | 2008-05-22 | Servicetec Japan Corp | Improver for color fastness and method for producing fiber dyed material |
| CN101619117A (en) * | 2008-07-03 | 2010-01-06 | 上海雅运纺织助剂有限公司 | Formaldehyde-free color fixing agent for reactive dyes and preparation method and application thereof |
| CN103555460A (en) * | 2013-11-04 | 2014-02-05 | 张家港市德宝化工有限公司 | Reactive dye anti-staining soaping agent and preparation method thereof |
| CN106749946A (en) * | 2016-12-02 | 2017-05-31 | 上海雅运纺织助剂有限公司 | Resistance to bubble fastness color fixing agent of reactive dye and its preparation method and application |
| CN108914630A (en) * | 2018-05-07 | 2018-11-30 | 东莞德永佳纺织制衣有限公司 | A kind of salt-free dyeing technique of cotton fabric |
-
2019
- 2019-04-30 CN CN201910360302.2A patent/CN110655609B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3472820A (en) * | 1964-06-19 | 1969-10-14 | Oreal | Polymercapto condensation polymers derived from maleic anhydride copolymers and aminothiols and their application for cosmetic purposes |
| US3549602A (en) * | 1964-06-19 | 1970-12-22 | Oreal | Polysulfhydryl polymers |
| US3576592A (en) * | 1965-02-23 | 1971-04-27 | Oreal | Process for permanently pressing textile articles made of keratinic fibers |
| JPH05321171A (en) * | 1992-05-19 | 1993-12-07 | Dai Ichi Kogyo Seiyaku Co Ltd | Fastness improver |
| JP2008115474A (en) * | 2006-10-31 | 2008-05-22 | Servicetec Japan Corp | Improver for color fastness and method for producing fiber dyed material |
| CN101619117A (en) * | 2008-07-03 | 2010-01-06 | 上海雅运纺织助剂有限公司 | Formaldehyde-free color fixing agent for reactive dyes and preparation method and application thereof |
| CN103555460A (en) * | 2013-11-04 | 2014-02-05 | 张家港市德宝化工有限公司 | Reactive dye anti-staining soaping agent and preparation method thereof |
| CN106749946A (en) * | 2016-12-02 | 2017-05-31 | 上海雅运纺织助剂有限公司 | Resistance to bubble fastness color fixing agent of reactive dye and its preparation method and application |
| CN108914630A (en) * | 2018-05-07 | 2018-11-30 | 东莞德永佳纺织制衣有限公司 | A kind of salt-free dyeing technique of cotton fabric |
Non-Patent Citations (4)
| Title |
|---|
| The Effect of Dyeing Properties of Fixing Agent and Plasma Treatment on Silk Fabric Dyed with Natural Dye Extract Obtained from Sambucus Ebulus L. Plant;Habip Dayioglu，等;《Procedia - Social and Behavioral Sciences》;20151231;第195卷;第1609-1617页 * |
| 固色剂的研究进展及展望;宋雪晶，等;《广东化工》;20111231;第38卷(第4期);第37-38页 * |
| 活性染料的结构与其活性染色性能的关系;武达机，等;《染料与染色》;20111031;第48卷(第5期);第16-20页 * |
| 羊毛低温染色助剂应用性能及作用机理研究;高普，等;《2013全国毛纺行业技术改造研讨会论文集》;20140820;第288-294页 * |
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