CN117646345A - Aldehyde-free color fixing agent and preparation method thereof - Google Patents
Aldehyde-free color fixing agent and preparation method thereof Download PDFInfo
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- CN117646345A CN117646345A CN202311636809.9A CN202311636809A CN117646345A CN 117646345 A CN117646345 A CN 117646345A CN 202311636809 A CN202311636809 A CN 202311636809A CN 117646345 A CN117646345 A CN 117646345A
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- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 97
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 66
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 22
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 22
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims description 106
- 229920001661 Chitosan Polymers 0.000 claims description 31
- 125000002091 cationic group Chemical group 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000010025 steaming Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- HGUZQMQXAHVIQC-UHFFFAOYSA-N n-methylethenamine Chemical compound CNC=C HGUZQMQXAHVIQC-UHFFFAOYSA-N 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 22
- 239000004744 fabric Substances 0.000 description 21
- 239000000975 dye Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000985 reactive dye Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- HFIYIRIMGZMCPC-UHFFFAOYSA-J chembl1326377 Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1N=NC1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-UHFFFAOYSA-J 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- -1 dimethane Chemical compound 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The application relates to the technical field of printing and dyeing fixing agents, and particularly discloses an aldehyde-free fixing agent and a preparation method thereof. The formaldehyde-free color fixing agent is prepared from the following raw materials in parts by weight: 81-162 parts of dimethyl diallyl ammonium chloride; 9-18 parts of acrylamide; 5-7 parts of ammonium persulfate; 55-105 parts of epichlorohydrin; 9-18 parts of tetraethylenepentamine; 4.5-9 parts of triethylamine; 9-18 parts of dimethylamine; 90-120 parts of water; 0.5-1 part of triallylamine; the dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate and epichlorohydrin are used for preparing a product A; the tetraethylenepentamine, triethylamine, dimethylamine and epichlorohydrin are used for preparing a product B; and mixing the product A, the product B, water and triallylamine to obtain the formaldehyde-free color fixing agent. The formaldehyde-free fixing agent disclosed by the application has the advantages of being compatible in permeability after application and reactive film forming property, and excellent in fixing performance.
Description
Technical Field
The application relates to the technical field of printing and dyeing fixing agents, in particular to an aldehyde-free fixing agent and a preparation method thereof.
Background
In the conventional dyeing process, the dye is combined with electrostatic action or physical adsorption on the surface of the fiber through the molecular formula structure, and the combination mode is not firm. The color fixing agent has the function of reducing washing and keeping color stable by making the combination mode between the dye and the fiber firmer through chemical reaction.
Generally, formaldehyde-containing fixing agents can cause harm to human bodies, so that in recent years, the requirements for formaldehyde-free fixing agents are continuously increased due to the related regulations of limiting the formaldehyde content on textiles in China, and researchers are beginning to develop various novel formaldehyde-free fixing agents. The formaldehyde-free fixing agent which is mainly used in the market at present is a cationic polymer type, adopts homo-polymerization and copolymerization of cationic monomers, and is applied to cotton fabrics as a reactive cationic fixing agent on the basis of preparing an epoxy group-containing cationic polymer P (DMDAAC-AGE) in the early stage. Meanwhile, the formaldehyde-free color fixing agent is more environment-friendly, and is not easy to cause toxicity and irritation to skin, so that the formaldehyde-free color fixing agent has a wide application prospect.
For the above related art, the inventor believes that there are some drawbacks in the application of the formaldehyde-free fixing agent at present, for example, in the process of using the formaldehyde-free fixing agent with reactive dye, the difference in self polymerization is often large, and the permeability and the reactive film forming property are difficult to be compatible, so that the fixation effect finally presented is poor, and therefore, a scheme is needed to solve the above technical problem.
Disclosure of Invention
In order to achieve the excellent effects of low residue and high fixation after the formaldehyde-free fixing agent is applied, the application provides the formaldehyde-free fixing agent and a preparation method thereof.
In a first aspect, the present application provides an aldehyde-free fixing agent, which adopts the following technical scheme:
the formaldehyde-free color fixing agent is prepared from the following raw materials in parts by weight:
81-162 parts of dimethyl diallyl ammonium chloride;
9-18 parts of acrylamide;
5-7 parts of ammonium persulfate;
55-105 parts of epichlorohydrin;
9-18 parts of tetraethylenepentamine;
4.5-9 parts of triethylamine;
9-18 parts of dimethylamine;
90-120 parts of water;
0.5-1 part of triallylamine;
the dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate and epichlorohydrin are used for preparing a product A;
the tetraethylenepentamine, triethylamine, dimethylamine and epichlorohydrin are used for preparing a product B;
and mixing the product A, the product B, water and triallylamine to obtain the formaldehyde-free color fixing agent.
By adopting the technical scheme, the product A prepared by taking the dimethyl diallyl ammonium chloride, the acrylamide, the ammonium persulfate and the epichlorohydrin as raw materials has small molecular weight and is easy to permeate, and can be effectively combined with dye and acts on fabrics; the product B prepared by taking tetraethylenepentamine, triethylamine, dimethylamine and epichlorohydrin as raw materials has larger molecular weight and good film forming property, improves the color fixing effect by utilizing the film forming of the reactive group on the surface of the fabric, and can further combine residual dye which is not reacted or reacted in the future due to the action of the product A; the triallylamine is added, so that after the color fixing agent is combined with the dye to act on the fabric, the fabric is shaped at high temperature, the crosslinking property is further improved, a three-dimensional net structure is formed, and a more excellent color fixing effect is achieved; according to the formaldehyde-free color fixing agent, through the collocation of the product A, the product B and the triallylamine, the formaldehyde-free color fixing agent not only has cationic groups and reactive groups, but also has the complex superposition reactivity among multiple components, so that the formaldehyde-free color fixing agent can be compatible in the permeability and the reactive film forming property after application, and has excellent color fixing performance.
Preferably, the molar ratio of the dimethyldiallylammonium chloride, the acrylamide and the epichlorohydrin is 9:1:0.8.
by adopting the technical scheme, the product A prepared from the raw materials in the molar ratio shows strong permeability, can keep better combination speed with dye, and further has better effect on printing and dyeing fabrics.
Preferably, the molar ratio of the tetraethylenepentamine to the triethylamine to the dimethylmethane to the epichlorohydrin is 1:0.5:1:5.
by adopting the technical scheme, the product B prepared from the raw materials in the molar ratio has better film forming property, and the matching effect with the product A is excellent and stable, so that the dye can be combined on the fabric more stably.
Preferably, the viscosity of the product A is 600-1200 mPas.
By adopting the technical scheme, the product A with the viscosity can be uniformly distributed on the surface of the fabric, and the product A enters a range of better permeability and quick combination with dye, and the product A is out of the viscosity range, so that the dispersion uniformity of the product A on the surface of the fabric is poor, and further the practical effect exerted by the application of the product A is lost.
Preferably, the viscosity of the product B is 18000-25000 mPa.s.
By adopting the technical scheme, the product B with the viscosity can be uniformly distributed on the surface of the fabric, so that better film forming property and quick combination property with residual dye are shown, and the product B can be degraded in dispersion uniformity on the surface of the fabric after exceeding the viscosity range, so that the loss of practical effect exerted by the application of the product B is caused.
Preferably, the raw material of the formaldehyde-free color fixing agent is further added with 4-8 parts by weight of cationic chitosan polymer, and the cationic chitosan polymer is prepared by the following steps:
s1, mixing N-methylvinylamine, [ (2-oxiranemethoxy) methyl ] -diethyl phosphonate and paraformaldehyde according to the molar ratio of 1 (1-1.2) (1-1.4), reacting at 55-90 ℃ for 30-90min, cooling, washing and rotary steaming to obtain an intermediate product;
s2, reacting the intermediate product and chloropropene in an acetone solvent according to the mole ratio of (1-1.2), wherein the reaction temperature is 40-60 ℃, the reaction time is 5-8 hours, and cooling, washing and rotary steaming are carried out to obtain a functional product;
s3, respectively dissolving chitosan and functional products in acetic acid solution and water according to a molar ratio of (4.8-5.4), then mixing, reacting at 60-80 ℃ for 7-10 hours, cooling, washing and rotary steaming to obtain the cationic chitosan polymer.
Through adopting the technical scheme, N-methyl vinylamine, [ (2-oxiranemethoxy) methyl ] -diethyl phosphonate and paraformaldehyde are reacted to form tertiary amine, then the tertiary amine reacts with chloropropene to carry out quaternization treatment, and finally epoxy groups of functional products and amino groups of chitosan are subjected to ring opening reaction to obtain cationic chitosan polymer; through a large amount of hydroxyl groups on the cationic chitosan polymer, hydrogen bonds can be formed with amino groups and hydroxyl groups of the dye, and simultaneously, the cationic active quaternary ammonium salt group is combined with sulfonic anions of the dye, so that the fixation effect of the formaldehyde-free fixation agent can be greatly improved.
In a second aspect, the present application provides a method for preparing an aldehyde-free fixing agent, which adopts the following technical scheme:
the preparation method of the formaldehyde-free color fixing agent comprises the following steps:
(1) Preparing raw materials comprising dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, epichlorohydrin, tetraethylenepentamine, triethylamine, dimethylamine, water and triallylamine according to a proportion;
(2) Uniformly mixing dimethyl diallyl ammonium chloride and acrylamide in the step (1), adding ammonium persulfate to perform a heating polymerization reaction, cooling after the reaction is finished, and adding 9.5-19.5 parts by weight of epichlorohydrin to perform a reaction to obtain a product A; uniformly mixing tetraethylenepentamine, triethylamine and dimethylamine in the step (1), and adding the rest parts by weight of epoxy chloropropane to react to obtain a product B;
(3) And (3) uniformly mixing the product A and the product B in the step (2) with water and triallylamine, and adjusting the pH value to obtain the formaldehyde-free color fixing agent.
By adopting the technical scheme, the preparation method is simple to operate and convenient for large-scale industrialized production popularization and application. Meanwhile, the preparation of the product A and the product B in the process is also beneficial to quality control of the obtained product A and the obtained product B, so that the finally obtained formaldehyde-free color fixing agent has excellent and stable quality.
Preferably, in the step (2), after uniformly mixing the dimethyldiallylammonium chloride and the acrylamide in the step (1), adding ammonium persulfate, heating to 60-90 ℃ for polymerization for 4-6 hours, adding 9.5-19.5 parts by weight of epichlorohydrin for reacting for 1.5-2.5 hours, raising the temperature to 40-60 ℃ and preserving the heat for 3-6 hours to obtain the product A.
By adopting the technical scheme, in the preparation of the product A, the parameter control is adopted, so that the raw materials of each component can be fully utilized in the reaction process, and further the product A with excellent and stable quality can be obtained.
Preferably, in the step (2), tetraethylenepentamine, triethylamine and dimethylamine in the step (1) are well mixed, and after the residual parts by weight of epichlorohydrin are added for reaction for 1.5-2.5 hours, the temperature is raised to 55-65 ℃ and the temperature is kept for 4.5-5.5 hours, so that the product B is obtained.
By adopting the technical scheme, in the preparation of the product B, the parameter control is adopted, so that the raw materials of all components can be stably matched in the reaction process, and further the product B with excellent and stable quality can be obtained.
Preferably, in the step (3), the product A and the product B in the step (2) are uniformly mixed with water and triallylamine, and the pH is regulated to 6-7, so that the formaldehyde-free color fixing agent can be obtained.
By adopting the technical scheme, the pH is adjusted to 6-7, so that the products A and B and water and triallylamine are kept in a relatively stable state, and the formaldehyde-free color fixing agent can be fully matched with the dye and acts on the fabric in the application process, so that an excellent effect can be exerted.
In summary, the present application has the following beneficial effects:
1. the product A prepared by taking dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate and epichlorohydrin as raw materials, the product B prepared by taking tetraethylenepentamine, triethylamine, dimethylamine and epichlorohydrin as raw materials, and the product A, the product B and triallyl amine are matched, so that the obtained formaldehyde-free color fixing agent can show excellent color fixing performance after being applied;
2. the cationic chitosan polymer is introduced into the raw material of the formaldehyde-free color fixing agent, so that the coordination effect between the color fixing agent and the dye can be enhanced, and the cationic chitosan polymer can be stably acted on the fabric to show better color fixing effect.
Detailed Description
The present application is described in further detail below with reference to examples.
Examples of preparation of starting materials and/or intermediates
Preparation example 1
A cationic chitosan polymer is prepared by the following steps:
s1, mixing N-methyl vinylamine, [ (2-oxiranemethoxy) methyl ] -diethyl phosphonate and paraformaldehyde according to a molar ratio of 1:1.1:1.2 for reaction at a temperature of 72.5 ℃ for 60min, and cooling, washing and rotary steaming to obtain an intermediate product;
s2, reacting the intermediate product and chloropropene in an acetone solvent according to a molar ratio of 1:1.1, wherein the reaction temperature is 50 ℃, the reaction time is 6.5 hours, and cooling, washing and rotary steaming are carried out to obtain a functional product;
s3, respectively dissolving chitosan and functional products in acetic acid solution and water according to a molar ratio of 1:5.1, then mixing, reacting at 70 ℃ for 8.5 hours, and cooling, washing and rotary steaming to obtain the cationic chitosan polymer.
Preparation example 2
A cationic chitosan polymer is prepared by the following steps:
s1, mixing N-methyl vinylamine, [ (2-oxiranemethoxy) methyl ] -diethyl phosphonate and paraformaldehyde according to a molar ratio of 1:1:1 for reaction at a temperature of 55 ℃ for 90min, and cooling, washing and rotary steaming to obtain an intermediate product;
s2, reacting the intermediate product and chloropropene in an acetone solvent according to a molar ratio of 1:1, wherein the reaction temperature is 40 ℃, the reaction time is 8 hours, and cooling, washing and rotary steaming are carried out to obtain a functional product;
s3, respectively dissolving chitosan and functional products in acetic acid solution and water according to a molar ratio of 1:4.8, then mixing, reacting at 60 ℃ for 10 hours, and cooling, washing and rotary steaming to obtain the cationic chitosan polymer.
Preparation example 3
A cationic chitosan polymer is prepared by the following steps:
s1, mixing N-methyl vinylamine, [ (2-oxiranemethoxy) methyl ] -diethyl phosphonate and paraformaldehyde according to a molar ratio of 1:1.2:1.4 for reaction at 90 ℃ for 30min, and cooling, washing and rotary steaming to obtain an intermediate product;
s2, reacting the intermediate product and chloropropene in an acetone solvent according to a molar ratio of 1:1.2, wherein the reaction temperature is 60 ℃, the reaction time is 5 hours, and cooling, washing and rotary steaming are carried out to obtain a functional product;
s3, respectively dissolving chitosan and functional products in acetic acid solution and water according to a molar ratio of 1:5.4, then mixing, reacting at 80 ℃ for 7 hours, and cooling, washing and rotary steaming to obtain the cationic chitosan polymer.
Examples
Example 1
The formaldehyde-free fixing agent is prepared from the following components and corresponding weights shown in table 1:
(1) Preparing raw materials comprising dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, epichlorohydrin, tetraethylenepentamine, triethylamine, dimethylamine, water and triallylamine according to a proportion;
(2) Uniformly mixing dimethyl diallyl ammonium chloride and acrylamide in the step (1), adding ammonium persulfate, heating to 75 ℃ for polymerization reaction for 5 hours, adding 9.5-19.5 parts by weight of epichlorohydrin for reaction 2, raising the temperature to 50 ℃ and preserving heat for 4.5 hours to obtain a product A; uniformly mixing tetraethylenepentamine, triethylamine and dimethylamine in the step (1), adding the rest parts by weight of epoxy chloropropane to react for 2 hours, and heating to 60 ℃ and preserving heat for 5 hours to obtain a product B;
(3) And (3) uniformly mixing the product A and the product B in the step (2), water and triallylamine, and adjusting the pH value to 6.5 to obtain the formaldehyde-free color fixing agent.
Note that: in the present example, 14.5 parts by weight of epichlorohydrin was added during the preparation of the product A; controlling the viscosity of the product A to 900 mPas; the viscosity of the product B was 21500 mPas.
Examples 2 to 3
An aldehyde-free fixing agent differs from example 1 in that the components and their respective weights are shown in table 1.
Table 1 Components in examples 1-3 and parts by weight (kg/part)
Example 4
The aldehyde-free color fixing agent is different from the embodiment 1 in that in the step (2), after the dimethyl diallyl ammonium chloride and the acrylamide in the step (1) are uniformly mixed, ammonium persulfate is added for polymerization reaction for 6 hours at 60 ℃, and finally 14.5 parts by weight of epichlorohydrin is added for reaction for 2.5 hours, and then the temperature is raised to 40 ℃ for 6 hours, so that a product A is obtained.
Example 5
The aldehyde-free color fixing agent is different from the embodiment 1 in that in the step (2), after the dimethyl diallyl ammonium chloride and the acrylamide in the step (1) are uniformly mixed, ammonium persulfate is added for polymerization reaction for 4 hours at 90 ℃, and finally 14.5 parts by weight of epichlorohydrin is added for reaction for 1.5 hours, and then the temperature is raised to 60 ℃ for 3 hours, so that a product A is obtained.
Example 6
The aldehyde-free color fixing agent is different from the embodiment 1 in that in the step (2), tetraethylenepentamine, triethylamine and dimethylamine in the step (1) are well mixed, the residual weight parts of epichlorohydrin are added for reaction for 1.5 hours, and then the temperature is raised to 55 ℃ for 4.5 hours, so that a product B is obtained.
Example 7
The aldehyde-free color fixing agent is different from the embodiment 1 in that in the step (2), tetraethylenepentamine, triethylamine and dimethylamine in the step (1) are well mixed, the residual weight part of epichlorohydrin is added for reaction for 2.5 hours, and then the temperature is raised to 65 ℃ and the temperature is kept for 5.5 hours, so that a product B is obtained.
Example 8
The difference from example 1 is that in step (3), the product A, the product B, water and triallylamine in step (2) are mixed uniformly, and the pH is adjusted to 6, so that the formaldehyde-free fixing agent is obtained.
Example 9
The difference from example 1 is that in step (3), the product A, the product B, water and triallylamine in step (2) are mixed uniformly, and the pH is adjusted to 7, so that the formaldehyde-free fixing agent is obtained.
Example 10
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product A is 600 mPas.
Example 11
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product A is 1200 mPa.s.
Example 12
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product A is 550 mPas.
Example 13
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product A is 1250 mPa.s.
Example 14
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product B is 18000 mPa.s.
Example 15
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product B is 25000 mPa.s.
Example 16
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product B is 17500 mPa.s.
Example 17
An aldehyde-free fixing agent differs from example 1 in that the viscosity of the product B is 25500 mPa.s.
Example 18
The aldehyde-free color fixing agent is different from the example 1 in that the total dosage of the dimethyldiallylammonium chloride, the acrylamide and the epichlorohydrin is unchanged, and the molar ratio of the three components is adjusted to be 9:1:0.8.
example 19
The aldehyde-free fixing agent is different from the example 1 in that the total dosage of tetraethylenepentamine, triethylamine, dimethyl ether and epichlorohydrin is unchanged, and the molar ratio of the four components is adjusted to be 1:0.5:1:5.
example 20
The aldehyde-free fixing agent is different from example 1 in that 6 parts by weight of cationic chitosan polymer is added to the raw material of the aldehyde-free fixing agent, the cationic chitosan polymer is obtained in preparation example 1, and the cationic chitosan polymer is mixed with a product A, a product B, water and triallylamine in step (3) for use.
Example 21
The aldehyde-free fixing agent is different from example 1 in that the cationic chitosan polymer is added in 4 parts by weight.
Example 22
The aldehyde-free fixing agent is different from example 1 in that the cationic chitosan polymer is added in 8 parts by weight.
Example 23
An aldehyde-free fixing agent differs from example 1 in that a cationic chitosan polymer was obtained in preparation example 2.
Example 24
An aldehyde-free fixing agent differs from example 1 in that a cationic chitosan polymer was obtained in preparation example 3.
Comparative example
Comparative example 1
An aldehyde-free fixing agent differs from example 1 in that the component of the aldehyde-free fixing agent does not contain product a.
Comparative example 2
An aldehyde-free fixing agent differs from example 1 in that the component of the aldehyde-free fixing agent does not contain product B.
Comparative example 3
An aldehyde-free fixing agent differs from example 1 in that the components of the aldehyde-free fixing agent do not contain product a and product B.
Comparative example 4
An aldehyde-free fixing agent differs from example 1 in that the components of the aldehyde-free fixing agent do not contain triallylamine.
Performance test samples: the aldehyde-free fixing agents obtained in examples 1 to 24 were used as test samples 1 to 24, and the aldehyde-free fixing agents obtained in comparative examples 1 to 4 were used as control samples 1 to 4.
The test method comprises the following steps: preparing test samples according to the following steps by using the test samples 1-24 and the control samples 1-4 respectively, and sequentially completing subsequent tests;
(1) All cotton fabrics were subjected to a bath ratio of 1 at 25 ℃): 20 is immersed into reactive dye, and is preserved for 10min, wherein the reactive dye consists of scarlet (C.I. reactive red 195) and dark blue (C.I. reactive black 5) according to the weight ratio of 5:1, and the dosage of the reactive dye is 4% o.w.f. (dye relative fabric weight);
(2) Heating to 80 ℃ at the speed of 2 ℃/min for dyeing, preserving heat for 20min, heating to 120 ℃ at the speed of 2 ℃/min, and preserving heat for 30min to obtain a coarse dyed fabric;
(3) And (3) carrying out dip color fixing treatment on the rough dyed fabric, wherein the dosage of a color fixing agent is 0.5% o.w.f (converted into content 40%, bath ratio is 1:20, temperature is 50 ℃ and time is 20min, and obtaining a test sample after cold water washing, dehydration and 90s shaping and drying at 150 ℃.
The test samples were tested as follows:
residual liquid after fixation: the residual liquid after fixation is compared, the lighter the color is, the higher the color fastness is (1-5 is used for representing the shade grade, 1 grade is best, and 5 grade is worst).
Residual liquid after water washing: and (3) cutting a test sample into a cloth sample to be tested with the size of 10cm multiplied by 4cm, marking, preparing 200ml of 2.0g/L washing powder solution, placing the cloth sample to be tested into the cloth sample, and placing the cloth sample at 100 ℃ for 5min, wherein the lighter the color of the observed residual liquid is, the higher the color fastness is (the light and dark grade is represented by 1-5, the best grade is 1 grade, and the worst grade is 5 grade).
Rubbing fastness test: HGT 4268-2011 determination of fixation effect of fixation agent for textile dyeing and finishing auxiliary cotton.
Wash fastness test: HGT 4268-2011 determination of fixation effect of fixation agent for textile dyeing and finishing auxiliary cotton.
TABLE 2 test results for test samples 1-24 and control samples 1-4
As can be seen from the combination of examples 1-3 and comparative examples 1-4, and table 2, the collocation of product a, product B and triallylamine enables the formaldehyde-free fixing agent to exhibit excellent fixing properties after application; if any one of the products A and B is matched with triallylamine, or only the products A and B are used for matching, the residual liquid after color fixation, the residual liquid after washing, the rubbing fastness and the washing fastness obtained by the test are all found to be poor, and the effect brought by matching the products A and B with triallylamine is far less excellent.
As can be seen from the combination of examples 1 and 10-13 and Table 2, the viscosity of the product A is 600-1200 mPa.s, which ensures stable performance of the application effect of the formaldehyde-free fixing agent, and the residual property is not deteriorated and the fixing effect is reduced when the viscosity exceeds the viscosity range. As can be seen from the combination of examples 1 and 14 to 17 and Table 2, the viscosity of the product B is 18000 to 25000 mPa.s, which ensures stable performance of the application effect of the formaldehyde-free fixing agent, and when the viscosity is beyond the above viscosity range, the residue is not deteriorated and the fixing effect is reduced.
As can be seen in combination with examples 1-3 and example 18 and with table 2, the molar ratio of dimethyldiallylammonium chloride, acrylamide, epichlorohydrin is 9:1: and 0.8, a product A with excellent and stable quality can be obtained, so that the finally obtained formaldehyde-free color fixing agent has a better application effect and outstanding color fixing performance. As can be seen in combination with examples 1-3 and example 19 and with table 2, the molar ratio of tetraethylenepentamine, triethylamine, dimethane, epichlorohydrin is 1:0.5:1: and 5, obtaining a product B with excellent and stable quality, and further enabling the finally obtained formaldehyde-free color fixing agent to show a better application effect and have outstanding color fixing performance.
It can be seen in combination with examples 1 and examples 20-24 and with table 2 that the introduction of cationic chitosan polymer into the raw material of the formaldehyde-free fixing agent can bring about a further improvement in low residue and high fixing properties, because the cationic chitosan polymer can enhance the effect of the fixation agent to the dye.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The formaldehyde-free color fixing agent is characterized by being prepared from the following raw materials in parts by weight:
81-162 parts of dimethyl diallyl ammonium chloride;
9-18 parts of acrylamide;
5-7 parts of ammonium persulfate;
55-105 parts of epichlorohydrin;
9-18 parts of tetraethylenepentamine;
4.5-9 parts of triethylamine;
9-18 parts of dimethylamine;
90-120 parts of water;
0.5-1 part of triallylamine;
the dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate and epichlorohydrin are used for preparing a product A;
the tetraethylenepentamine, triethylamine, dimethylamine and epichlorohydrin are used for preparing a product B;
and mixing the product A, the product B, water and triallylamine to obtain the formaldehyde-free color fixing agent.
2. The formaldehyde-free fixing agent of claim 1, wherein: the molar ratio of the dimethyl diallyl ammonium chloride, the acrylamide and the epichlorohydrin is 9:1:0.8.
3. the formaldehyde-free fixing agent of claim 1, wherein: the molar ratio of the tetraethylenepentamine to the triethylamine to the dimethylmethane to the epichlorohydrin is 1:0.5:1:5.
4. the formaldehyde-free fixing agent of claim 1, wherein: the viscosity of the product A is 600-1200 mPa.s.
5. The formaldehyde-free fixing agent of claim 1, wherein: the viscosity of the product B is 18000-25000 mPa.s.
6. The formaldehyde-free fixing agent of claim 1, wherein: the raw materials of the formaldehyde-free color fixing agent are also added with 4-8 parts by weight of cationic chitosan polymer, and the cationic chitosan polymer is prepared by the following steps:
s1, mixing N-methylvinylamine, [ (2-oxiranemethoxy) methyl ] -diethyl phosphonate and paraformaldehyde according to the molar ratio of 1 (1-1.2) (1-1.4), reacting at 55-90 ℃ for 30-90min, cooling, washing and rotary steaming to obtain an intermediate product;
s2, reacting the intermediate product and chloropropene in an acetone solvent according to the mole ratio of (1-1.2), wherein the reaction temperature is 40-60 ℃, the reaction time is 5-8 hours, and cooling, washing and rotary steaming are carried out to obtain a functional product;
s3, respectively dissolving chitosan and functional products in acetic acid solution and water according to a molar ratio of (4.8-5.4), then mixing, reacting at 60-80 ℃ for 7-10 hours, cooling, washing and rotary steaming to obtain the cationic chitosan polymer.
7. The method for preparing the formaldehyde-free fixing agent according to claim 1, which is characterized in that: the method comprises the following steps:
(1) Preparing raw materials comprising dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, epichlorohydrin, tetraethylenepentamine, triethylamine, dimethylamine, water and triallylamine according to a proportion;
(2) Uniformly mixing dimethyl diallyl ammonium chloride and acrylamide in the step (1), adding ammonium persulfate to perform a heating polymerization reaction, cooling after the reaction is finished, and adding 9.5-19.5 parts by weight of epichlorohydrin to perform a reaction to obtain a product A; uniformly mixing tetraethylenepentamine, triethylamine and dimethylamine in the step (1), and adding the rest parts by weight of epoxy chloropropane to react to obtain a product B;
(3) And (3) uniformly mixing the product A and the product B in the step (2) with water and triallylamine, and adjusting the pH value to obtain the formaldehyde-free color fixing agent.
8. The method for preparing the formaldehyde-free fixing agent according to claim 7, characterized in that: in the step (2), after uniformly mixing the dimethyldiallylammonium chloride and the acrylamide in the step (1), adding ammonium persulfate, heating to 60-90 ℃ for polymerization for 4-6 hours, adding 9.5-19.5 parts by weight of epichlorohydrin for reaction for 1.5-2.5 hours, raising the temperature to 40-60 ℃ and preserving the heat for 3-6 hours to obtain a product A.
9. The method for preparing the formaldehyde-free fixing agent according to claim 7, characterized in that: in the step (2), tetraethylenepentamine, triethylamine and dimethylamine in the step (1) are well mixed, and after the residual parts by weight of epoxy chloropropane are added for reaction for 1.5-2.5 hours, the temperature is raised to 55-65 ℃ and the temperature is kept for 4.5-5.5 hours, so that a product B is obtained.
10. The method for preparing the formaldehyde-free fixing agent according to claim 7, characterized in that: in the step (3), the product A and the product B in the step (2) are uniformly mixed with water and triallylamine, and the pH is regulated to 6-7, so that the formaldehyde-free color fixing agent can be obtained.
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