CN115748271B - Ternary polymerization efficient formaldehyde-free color fixing agent for reactive dye and preparation method thereof - Google Patents
Ternary polymerization efficient formaldehyde-free color fixing agent for reactive dye and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 239000000985 reactive dye Substances 0.000 title claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 41
- 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 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 16
- 125000002091 cationic group Chemical group 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- -1 acyloxy cations Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 5
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 claims description 4
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 4
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000975 dye Substances 0.000 abstract description 11
- 239000004744 fabric Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 6
- 229920002678 cellulose Polymers 0.000 abstract description 4
- 239000001913 cellulose Substances 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000010186 staining Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 1
- GKUYJMDCOJTUTB-UHFFFAOYSA-M [NH4+].[Na+].[O-]S([O-])=O Chemical group [NH4+].[Na+].[O-]S([O-])=O GKUYJMDCOJTUTB-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CRGOPMLUWCMMCK-UHFFFAOYSA-M benzyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)CC1=CC=CC=C1 CRGOPMLUWCMMCK-UHFFFAOYSA-M 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The invention provides a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes and a preparation method thereof, and belongs to the technical field of color fixing agents. The efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye is prepared from the following raw materials in parts by weight: 60 to 75 parts of dimethyl diallyl ammonium chloride solution, 1.0 to 7.0 parts of acyloxy-containing cationic monomer, 5.0 to 12.0 parts of cross-linking agent, 0.1 to 0.5 parts of initiator and 10 to 25 parts of deionized water. The ternary polymerization high-efficiency formaldehyde-free color fixing agent is low in cost, high in efficiency and environment-friendly, and can better form complex lake with anionic dye due to strong cationic property. By introducing active acyloxy, the reactive acyloxy can react with the active groups on dye molecules and active hydrogen on cellulose molecules respectively, so that the dye and the fiber are combined more tightly, and the color-fixed fabric has excellent washing fastness, color-staining fastness and dry-wet rubbing color fastness.
Description
Technical Field
The invention belongs to the technical field of color fixing agents, and particularly relates to a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes and a preparation method thereof.
Background
The textile industry is the traditional industry in China, plays a role in national economy development, and the color fixing agent is one of important auxiliary agents indispensable in the printing and dyeing industry. In recent years, some developed countries are reverse trade, and the quality requirements of textile products are continuously improved, wherein the most important are the requirements on the color fastness of textiles and the strict limitation on the free formaldehyde content.
CN103696296B discloses a cationic formaldehyde-free fixing agent for reactive dye and a preparation method thereof, which is mainly prepared from dimethyl diallyl ammonium chloride, tertiary amino-containing monomers and a cross-linking agent. By introducing active groups such as tertiary amino groups, ester groups and the like to react with reactive groups on dye molecules and hydroxyl groups on cellulose molecules, the combination of the dye molecules and fibers is firmer, so that the dry and wet rubbing fastness and the washing fastness are improved. However, the introduction of tertiary amino groups can improve the fixation effect of the fixing agent, but the phenomenon of yellowing of the fabric after fixation can occur.
CN106811998B discloses a cross-linking formaldehyde-free fixing agent emulsion and its preparation method, mainly prepared from dimethyl diallyl ammonium chloride monomer, diallyl amine hydrochloride monomer, chelating agent, organic alkane solvent, emulsion stabilizer, emulsifying agent, oil-soluble thermal initiator and active activator through inverse emulsion polymerization process, during the preparation process, the organic alkane solvent is added to disperse the monomer into fine bead particles through emulsification for polymerization. The method can obtain cross-linking formaldehyde-free color fixing agent emulsion with different cross-linking degrees and different molecular weights, but the method is complex in process, high in cost and not in accordance with the current environment-friendly concept.
Dimethyl diallyl ammonium chloride is an ideal color fixing agent raw material, is nontoxic and pollution-free, meets the requirements of green environmental protection, and has lower price compared with other quaternary ammonium salt cationic monomers. However, the polydimethyl diallyl ammonium chloride color fixing agent has the problems of poor wet rubbing fastness, poor washing fastness and the like.
Disclosure of Invention
The invention provides a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes and a preparation method thereof, and aims to solve the technical problems.
The invention provides a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes, which is prepared from the following raw materials in parts by weight: 60 to 75 parts of dimethyl diallyl ammonium chloride solution, 1.0 to 7.0 parts of acyloxy-containing cationic monomer, 5.0 to 12.0 parts of cross-linking agent, 0.1 to 0.5 parts of initiator and 10 to 25 parts of deionized water.
Further, the mass percentage concentration of the dimethyl diallyl ammonium chloride solution is 50-65%.
Further, the cation monomer containing acyloxy is at least one of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, methacryloxyethyl dimethyl benzyl ammonium chloride and acryloxyethyl dimethyl benzyl ammonium chloride.
Further, the cross-linking agent is at least one of diallyl amine, triallyl amine and N-methyldiallyl amine.
Further, the initiator is at least one of redox systems formed by sodium sulfite, ammonium persulfate, potassium persulfate and sodium persulfate.
Further, the required amount of the negative charges is 600-700 ueq/L, the viscosity average molecular weight is 10-30 ten thousand, the pH is 5-7, the sugar degree is 58-62%, and the dynamic viscosity is 5000-15000 mpa.s.
The embodiment of the invention also provides a preparation method of the ternary polymerization high-efficiency formaldehyde-free color fixing agent for any reactive dye, which comprises the following steps:
Mixing deionized water and an initiator to obtain an initiator solution;
Under the condition of nitrogen, adding 1/5 to 1/4 of the total mass of the dimethyl diallyl ammonium chloride solution into a reaction kettle, stirring and heating to 70 to 80 ℃;
Starting to dropwise add the rest dimethyl diallyl ammonium chloride solution;
simultaneously, adding an acyloxy-containing cationic monomer and a crosslinking agent in a second dropwise manner;
Meanwhile, the third dripping is carried out by 1/5 of the total amount of the initiator solution, and the temperature is raised to 85-95 ℃ after the dripping is finished;
fourthly, dropwise adding 2/5 of the total amount of the initiator solution, preserving heat for 2-3 hours, and then heating to 95-105 ℃;
And fifthly, dropwise adding 2/5 of the total amount of the initiator solution, preserving heat for 2-3h, cooling to 40 ℃, and discharging to obtain the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye.
Further, the first dripping time is 1-3h; the second dripping time is 0.5-1h.
Further, the third dripping time is 2-4h; the fourth dripping time is 1-2h; the time of the fifth drop is 1-2h.
The invention has the following advantages:
The ternary polymerization high-efficiency formaldehyde-free color fixing agent provided by the invention is low in cost, high in efficiency and environment-friendly, and can better form complex lake with anionic dye due to strong cationic property. By introducing active acyloxy, the reactive acyloxy can react with the active groups on dye molecules and active hydrogen on cellulose molecules respectively, so that the dye and the fiber are combined more tightly, and the color-fixed fabric has excellent washing fastness, color-staining fastness and dry-wet rubbing color fastness. In addition, a small amount of cross-linking agent is added, the molecular film forming property of the color fixing agent after micro cross-linking is better, and the color fixing effect of the color fixing agent is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. Embodiments of the invention and features of the embodiments may be combined with each other without conflict.
The embodiment of the invention provides a ternary polymerization high-efficiency formaldehyde-free color fixing agent for reactive dyes, which is prepared from the following raw materials in parts by weight: 60 to 75 parts of dimethyl diallyl ammonium chloride solution, 1.0 to 7.0 parts of acyloxy-containing cationic monomer, 5.0 to 12.0 parts of cross-linking agent, 0.1 to 0.5 parts of initiator and 10 to 25 parts of deionized water.
The ternary polymerization high-efficiency formaldehyde-free color fixing agent for the reactive dye provided by the embodiment of the invention has stronger cationic property, and can better form complex lake with anionic dye; by introducing active acyloxy, the reactive acyloxy can react with the active groups on dye molecules and active hydrogen on cellulose molecules respectively, so that the dye and the fiber are combined more tightly, and the color-fixed fabric has excellent washing fastness, color-staining fastness and dry-wet rubbing color fastness. In addition, a small amount of cross-linking agent is added, the molecular film forming property of the color fixing agent after micro cross-linking is better, and the color fixing effect of the color fixing agent is further improved.
In one embodiment of the invention, the concentration of the dimethyl diallyl ammonium chloride solution is 50-65% by mass. Preferably, the mass percentage concentration of the dimethyl diallyl ammonium chloride solution is 60%.
In an embodiment of the present invention, the monomer containing an acyloxy cation is at least one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl benzyl ammonium chloride, and acryloyloxyethyl dimethyl benzyl ammonium chloride. Preferably, the acyloxy-containing cationic monomer is methacryloyloxyethyl trimethylammonium chloride.
In an embodiment of the present invention, the crosslinking agent is at least one of diallylamine, triallylamine, and N-methyldiallylamine. Preferably, the crosslinking agent is diallylamine.
In an embodiment of the present invention, the initiator is at least one of sodium sulfite and a redox system formed by ammonium persulfate, potassium persulfate and sodium persulfate. Preferably, the initiator is a sodium sulfite-ammonium persulfate redox system.
Wherein the molar ratio of sodium sulfite to ammonium persulfate, potassium persulfate or sodium persulfate is 1:1.
In one embodiment of the invention, the obtained ternary polymerization efficient formaldehyde-free color fixing agent for reactive dye has the required negative charge amount of 600-700 ueq/L, the viscosity average molecular weight of 10-30 ten thousand, the pH of 5-7, the sugar degree of 58-62 percent and the dynamic viscosity of 5000-15000 mpa.s.
The embodiment of the invention also provides a preparation method of the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye, which comprises the following steps:
Mixing deionized water and an initiator to obtain an initiator solution;
Under the condition of nitrogen, adding 1/5 to 1/4 of the total mass of the dimethyl diallyl ammonium chloride solution into a reaction kettle, stirring and heating to 70 to 80 ℃;
Starting to dropwise add the rest dimethyl diallyl ammonium chloride solution;
simultaneously, adding an acyloxy-containing cationic monomer and a crosslinking agent in a second dropwise manner;
Meanwhile, the third dripping is carried out by 1/5 of the total amount of the initiator solution, and the temperature is raised to 85-95 ℃ after the dripping is finished;
fourthly, dropwise adding 2/5 of the total amount of the initiator solution, preserving heat for 2-3 hours, and then heating to 95-105 ℃;
And fifthly, dropwise adding 2/5 of the total amount of the initiator solution, preserving heat for 2-3h, cooling to 40 ℃, and discharging to obtain the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye.
According to the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye, provided by the embodiment of the invention, the initiator is added for multiple times, so that the polymerization reaction is more sufficient, the monomer conversion rate is improved, and the color fixing effect is further improved.
In one embodiment of the invention, the first dripping time is 1-3 hours; the second dripping time is 0.5-1h.
In one embodiment of the invention, the third dripping time is 2-4 hours; the fourth dripping time is 1-2h; the time of the fifth drop is 1-2h.
The ternary polymerization high-efficiency formaldehyde-free color fixing agent for the reactive dye provided by the embodiment of the invention can be used for fixing colors of various fabrics dyed by the reactive dye in textile industry, and the fabrics after the color fixing have excellent washing fastness, color fastness and dry and wet rubbing color fastness.
The invention will be described in detail with reference to examples.
The whole reaction process is carried out in a stainless steel normal pressure reaction kettle which is replaced by nitrogen and is provided with a stirrer and can control the temperature. In the examples and comparative examples, all materials were calculated in mass fraction.
Example 1a preparation method of a ternary polymerization efficient formaldehyde-free fixing agent for reactive dyes comprises the following steps:
13.4 parts of deionized water and 0.5 part of initiator (sodium sulfite and ammonium persulfate are mixed according to the mol ratio of 1:1) to obtain an initiator solution;
under the condition of nitrogen, adding 75 parts of 1/5 of the total mass of the dimethyldiallylammonium chloride solution with the mass percentage concentration of 60 percent into a reaction kettle, stirring and heating to 75 ℃;
Starting a first dropwise addition (time is 1.5 h) of the rest dimethyl diallyl ammonium chloride solution;
simultaneously, 6 parts of monomer containing acyloxy cations (methacryloyloxyethyl dimethyl benzyl ammonium chloride) and 8 parts of cross-linking agent (diallyl amine) are added dropwise (time is 0.7 h);
Meanwhile, the third dripping (the time is 3 h) is 1/5 of the total amount of the initiator solution, and the temperature is raised to 90 ℃ after the dripping is finished;
Fourthly, dropwise adding (the time is 1.5 h) 2/5 of the total amount of the initiator solution, and heating to 100 ℃ after heat preservation for 2-3 h;
and fifthly, dropwise adding (the time is 1.5 h) 2/5 of the total amount of the initiator solution, preserving heat for 2-3h, cooling to 40 ℃, and discharging to obtain the efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye.
The performance of the ternary polymerization high-efficiency formaldehyde-free color fixing agent for the reactive dye is measured according to a national standard detection method, and finally the reactive dye is obtained: the charge demand was 613. Mu. Eq/L, the viscosity average molecular weight was 15.23 ten thousand, the sugar degree was 60.0%, and the dynamic viscosity was 5143 mpa.s.
Example 2a preparation method of a ternary polymerization efficient formaldehyde-free fixing agent for reactive dyes comprises the following steps:
Mixing 20 parts of deionized water and 0.2 part of an initiator (sodium sulfite and potassium persulfate according to a molar ratio of 1:1) to obtain an initiator solution;
Under the condition of nitrogen, adding 72.5 parts by mass of 1/4 of the total mass of the dimethyldiallylammonium chloride solution with the mass percentage concentration of 60 percent into a reaction kettle, stirring and heating to 80 ℃;
starting a first dropwise adding (3 h) of the rest dimethyl diallyl ammonium chloride solution;
Simultaneously, 5 parts of monomer containing acyloxy cations (methacryloyloxyethyl trimethyl ammonium chloride) and 10 parts of cross-linking agent (triallylamine) are added dropwise (time is 1 h);
Meanwhile, the third dripping (the time is 4 h) is 1/5 of the total amount of the initiator solution, and the temperature is raised to 95 ℃ after the dripping is finished;
fourthly, dropwise adding (the time is 2 h) 2/5 of the total amount of the initiator solution, and heating to 105 ℃ after heat preservation for 2-3 h;
And fifthly, dropwise adding (the time is 2 h) 2/5 of the total amount of the initiator solution, preserving heat for 2-3h, cooling to 40 ℃, and discharging to obtain the efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye.
The performance of the ternary polymerization high-efficiency formaldehyde-free color fixing agent for the reactive dye is measured according to a national standard detection method, and finally the reactive dye is obtained: the charge requirement is 627 mu eq/L, the viscosity average molecular weight is 16.31 ten thousand, the sugar degree is 60.8%, and the dynamic viscosity is 11851 mpa.s.
Example 3
A preparation method of a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes comprises the following steps:
Mixing 16 parts of deionized water and 0.4 part of an initiator (sodium sulfite and sodium persulfate according to a molar ratio of 1:1) to obtain an initiator solution;
under the condition of nitrogen, 73 parts of dimethyl diallyl ammonium chloride solution with the mass percentage concentration of 62% is added into a reaction kettle, and the mixture is stirred and heated to 70 ℃;
starting a first dropwise adding (time is 12 h) of the rest dimethyl diallyl ammonium chloride solution;
Simultaneously, 4 parts of monomer containing acyloxy cations (acryloyloxyethyl trimethyl ammonium chloride) and 10 parts of cross-linking agent (N-methyldiallyl amine) are added dropwise (the time is 0.6 h);
meanwhile, the third dripping (the time is 2 h) is 1/5 of the total amount of the initiator solution, and the temperature is raised to 85 ℃ after the dripping is finished;
fourthly, dropwise adding (the time is 1 h) 2/5 of the total amount of the initiator solution, and heating to 95 ℃ after heat preservation for 2-3 h;
And fifthly, dropwise adding (the time is 1 h) 2/5 of the total amount of the initiator solution, preserving heat for 2-3h, cooling to 40 ℃, and discharging to obtain the efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye.
The performance of the ternary polymerization high-efficiency formaldehyde-free color fixing agent for the reactive dye is measured according to a national standard detection method, and finally the reactive dye is obtained: the charge demand was 623. Mu. Eq/L, the viscosity average molecular weight was 20.85 ten thousand, the sugar degree was 59% and the dynamic viscosity was 9027 mpa.s.
Comparative example 1
The difference is that no acyloxy group-containing cationic monomer was added as in example 1.
The performance of the formaldehyde-free fixing agent is measured according to a national standard detection method, and finally the formaldehyde-free fixing agent is obtained: the charge demand was 525. Mu. Eq/L, the viscosity average molecular weight was 15.32 ten thousand, the sugar degree was 61.3% and the dynamic viscosity was 10235 mpa.s.
Comparative example 2
The same as in example 1, except that the dimethyl diallyl ammonium chloride solution was completely added to the reaction vessel under nitrogen, and then stirred and heated; and all initiator solutions are added dropwise during the third addition.
The performance of the formaldehyde-free fixing agent is measured according to a national standard detection method, and finally the formaldehyde-free fixing agent is obtained: the charge requirement was 554. Mu. Eq/L, the viscosity average molecular weight was 13.27 ten thousand, the sugar degree was 61.1% and the dynamic viscosity was 9736 mpa.s.
Test example 1
The cotton fabric dyed by the active scarlet CMCRea. Red194 is treated with the high-efficiency formaldehyde-free fixing agent prepared in examples 1-3 and comparative examples 1-2, and the fixing agent is used in an amount of 1% (o.w.f), pH is 5-7, bath ratio is 1:10, temperature is 40 ℃ and time is 30min.
The performance of the cotton fabric after fixation is detected according to the national standard detection method, and the main performance indexes are shown in table 1.
TABLE 1
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. The preparation method of the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye is characterized by comprising the following steps of:
Mixing deionized water and an initiator to obtain an initiator solution;
Under the condition of nitrogen, adding 1/5 to 1/4 of the total mass of the dimethyl diallyl ammonium chloride solution into a reaction kettle, stirring and heating to 70 to 80 ℃;
Starting to dropwise add the rest dimethyl diallyl ammonium chloride solution;
simultaneously, adding an acyloxy-containing cationic monomer and a crosslinking agent in a second dropwise manner;
Meanwhile, the third dripping is carried out by 1/5 of the total amount of the initiator solution, and the temperature is raised to 85-95 ℃ after the dripping is finished;
fourthly, dropwise adding 2/5 of the total amount of the initiator solution, preserving heat for 2-3 hours, and then heating to 95-105 ℃;
fifthly, dropwise adding 2/5 of the total amount of the initiator solution, preserving heat for 2-3h, cooling to 40 ℃, and discharging to obtain the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye;
The ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye is prepared from the following raw materials in parts by weight: 60 to 75 parts of dimethyl diallyl ammonium chloride solution, 1.0 to 7.0 parts of acyloxy-containing cationic monomer, 5.0 to 12.0 parts of cross-linking agent, 0.1 to 0.5 parts of initiator and 10 to 25 parts of deionized water;
the monomer containing acyloxy cations is at least one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl benzyl ammonium chloride and acryloyloxyethyl dimethyl benzyl ammonium chloride;
the cross-linking agent is at least one of diallyl amine, triallyl amine and N-methyldiallyl amine;
The initiator is at least one of redox systems formed by sodium sulfite, ammonium persulfate, potassium persulfate and sodium persulfate.
2. The method according to claim 1, wherein,
The mass percentage concentration of the dimethyl diallyl ammonium chloride solution is 50-65%.
3. The method according to claim 1, wherein,
The required amount of negative charges is 600-700 ueq/L, the viscosity average molecular weight is 10-30 ten thousand, the pH is 5-7, the sugar degree is 58-62%, and the dynamic viscosity is 5000-15000 mpa.s.
4. The method according to claim 1, wherein,
The first dripping time is 1-3h; the second dripping time is 0.5-1h.
5. The method according to claim 1, wherein,
The third dripping time is 2-4h; the fourth dripping time is 1-2h; the time of the fifth drop is 1-2h.
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