CN115748271A - 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 53
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 37
- 239000000985 reactive dye Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 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 25
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 125000002091 cationic group Chemical group 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 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
- 238000010438 heat treatment Methods 0.000 claims description 17
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 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 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000002156 mixing 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
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims 2
- 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
- 238000010186 staining Methods 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
- 238000001514 detection method Methods 0.000 description 6
- 238000000034 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
- 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
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-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
- 239000002738 chelating agent 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000001737 promoting effect Effects 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Abstract
The invention provides a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes and a preparation method thereof, belonging to the technical field of color fixing agents. The ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye is prepared from the following raw materials in parts by weight: 60-75 parts of dimethyl diallyl ammonium chloride solution, 1.0-7.0 parts of acyloxy-containing cationic monomer, 5.0-12.0 parts of cross-linking agent, 0.1-0.5 part of initiator and 10-25 parts of deionized water. The ternary polymerization efficient formaldehyde-free color fixing agent disclosed by the invention is low in cost, efficient and environment-friendly, and can better form complex color lake with anionic dye due to stronger cationic property. By introducing the active group acyloxy, the reactive group acyloxy can respectively react with the active group on the dye molecule and the active hydrogen on the cellulose molecule, so that the dye and the fiber are combined more tightly, and the color-fixed fabric has excellent washing fastness, 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 a reactive dye and a preparation method thereof.
Background
The textile industry is the traditional industry in China, plays a role in promoting the importance of national economy development, and the color fixing agent is one of the indispensable important auxiliary agents in the printing and dyeing industry. In recent years, in order to reverse trade, the quality requirements of textile products are continuously improved in some developed countries, and above all, the requirements on the color fastness of textiles and the strict limitation on the content of free formaldehyde are required.
CN103696296B discloses a cationic formaldehyde-free color fixing agent for reactive dyes and a preparation method thereof, and the cationic formaldehyde-free color fixing agent is mainly prepared from dimethyl diallyl ammonium chloride, a tertiary amino group-containing monomer and a crosslinking agent. The combination of the dye molecules and the fiber is firmer by introducing active groups such as tertiary amino, ester groups and the like to react with reactive groups on the dye molecules and hydroxyl on the cellulose molecules, thereby improving the dry and wet rubbing fastness and the color fastness to washing. However, the introduction of tertiary amino groups can improve the fixation effect of the fixing agent, but yellowing of the fabric occurs after fixation.
CN106811998B discloses a cross-linking formaldehyde-free fixing agent emulsion and a preparation method thereof, which is mainly prepared from a dimethyldiallylammonium chloride monomer, a diallylamine hydrochloride monomer, a chelating agent, an organic alkane solvent, an emulsion stabilizer, an emulsifier, an oil-soluble thermal initiator and an active activator by an inverse emulsion polymerization process, wherein in the preparation process, the organic alkane solvent is added to disperse the monomers into fine bead-shaped particles for polymerization through emulsification. The method can obtain the crosslinking formaldehyde-free color fixing agent emulsion with different crosslinking degrees and different molecular weights, but the method has complex process and higher cost, and does not accord with the current concept of environmental protection.
The dimethyl diallyl ammonium chloride is an ideal raw material of the fixing agent, is non-toxic and pollution-free, meets the requirement of green environmental protection, and has lower price compared with other quaternary ammonium salt cationic monomers. But the poly dimethyl diallyl ammonium chloride color fixing agent has the problems of poor wet rubbing fastness, poor color fastness to washing 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: 60-75 parts of dimethyl diallyl ammonium chloride solution, 1.0-7.0 parts of acyloxy-containing cationic monomer, 5.0-12.0 parts of cross-linking agent, 0.1-0.5 part of initiator and 10-25 parts of deionized water.
Further, the mass percentage concentration of the dimethyl diallyl ammonium chloride solution is 50-65%.
Further, the acyloxy-containing cationic monomer is at least one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl benzyl ammonium chloride and acryloyloxyethyl dimethyl benzyl ammonium chloride.
Further, the crosslinking agent is at least one of diallylamine, triallylamine and N-methyldiallylamine.
Further, the initiator is at least one of redox systems formed by sodium sulfite, ammonium persulfate, potassium persulfate and sodium persulfate.
Furthermore, the negative charge demand 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 efficient 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;
adding 1/5-1/4 of the total mass of the dimethyl diallyl ammonium chloride solution into a reaction kettle under the condition of nitrogen, and stirring and heating to 70-80 ℃;
starting the first addition of the remaining dimethyldiallylammonium chloride solution;
simultaneously, secondly dropping acyloxy-containing cationic monomer and cross-linking agent;
simultaneously, adding 1/5 of the total amount of the initiator solution dropwise, and heating to 85-95 ℃ after dropwise adding;
fourthly, dripping 2/5 of the total amount of the initiator solution, preserving the heat for 2-3h, and then heating to 95-105 ℃;
fifthly, dripping 2/5 of the total amount of the initiator solution, preserving the 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 time of the second dripping is 0.5-1h.
Further, the third dripping time is 2-4h; the fourth dripping time is 1-2h; the fifth dripping time is 1-2h.
The invention has the following advantages:
the ternary polymerization efficient formaldehyde-free color fixing agent provided by the invention is low in cost, efficient and environment-friendly, and can better form complex lake with anionic dye due to strong cationic property. By introducing the active group acyloxy, the reactive group acyloxy can respectively react with the active group on the dye molecule and the active hydrogen on the cellulose molecule, so that the dye and the fiber are combined more tightly, and the fixed fabric has excellent washing fastness, staining fastness and dry-wet rubbing color fastness. In addition, a small amount of cross-linking agent is added, the film forming property of the molecules of the color fixing agent after micro-crosslinking is better, and the color fixing effect of the color fixing agent is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the invention may be combined with each other without conflict.
The embodiment of 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: 60-75 parts of dimethyl diallyl ammonium chloride solution, 1.0-7.0 parts of acyloxy-containing cationic monomer, 5.0-12.0 parts of cross-linking agent, 0.1-0.5 part of initiator and 10-25 parts of deionized water.
The ternary polymerization efficient 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 the active group acyloxy, the reactive group acyloxy can respectively react with the active group on the dye molecule and the active hydrogen on the cellulose molecule, so that the dye and the fiber are combined more tightly, and the color-fixed fabric has excellent washing fastness, staining fastness and dry-wet rubbing color fastness. In addition, a small amount of cross-linking agent is added, the film forming property of the molecules of the color fixing agent after micro-crosslinking is better, and the color fixing effect of the color fixing agent is further improved.
In one embodiment of the invention, the mass percentage concentration of the dimethyldiallylammonium chloride solution is 50-65%. Preferably, the mass percentage concentration of the dimethyldiallylammonium chloride solution is 60%.
In an embodiment of the present invention, the acyloxy-containing cationic monomer 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 group-containing cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride.
In one 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 one embodiment of the invention, the initiator is at least one of redox systems formed by sodium sulfite and ammonium persulfate, potassium persulfate and sodium persulfate. Preferably, the initiator is a sodium sulfite-ammonium persulfate redox system.
Wherein the molar ratio of the sodium sulfite to the ammonium persulfate, the potassium persulfate or the sodium persulfate is 1.
In one embodiment of the invention, the negative charge demand of the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye is 600-700 ueq/L, the viscosity average molecular weight is 10-30 ten thousand, the pH value is 5-7, the sugar degree is 58-62%, and the dynamic viscosity is 5000-15000 mpa · s.
An embodiment of the present invention further provides a preparation method of the ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes, which comprises the following steps:
mixing deionized water and an initiator to obtain an initiator solution;
adding 1/5-1/4 of the total mass of the dimethyl diallyl ammonium chloride solution into a reaction kettle under the condition of nitrogen, stirring and heating to 70-80 ℃;
starting the first addition of the remaining dimethyldiallylammonium chloride solution;
simultaneously, adding an acyloxy-containing cationic monomer and a cross-linking agent dropwise;
simultaneously, adding 1/5 of the total amount of the initiator solution dropwise, and heating to 85-95 ℃ after dropwise adding;
fourthly, dripping 2/5 of the total amount of the initiator solution, preserving the heat for 2-3h, and then heating to 95-105 ℃;
fifthly, dripping 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 favorably improved, and the color fixing effect is further improved.
In one embodiment of the invention, the first dripping time is 1-3h; the time of the second dripping is 0.5-1h.
In one embodiment of the invention, the third dropwise adding time is 2-4h; the fourth dripping time is 1-2h; the fifth dripping time is 1-2h.
The application of the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye provided by the embodiment of the invention can be used for fixing various reactive dye dyed fabrics in the textile industry, and the fixed fabrics have excellent washing fastness, staining fastness and dry-wet rubbing color fastness.
The present 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, is provided with a stirrer and can control the temperature. In the examples and comparative examples, all materials are in mass fraction.
Example 1A preparation method of a ternary polymerization efficient formaldehyde-free color fixing agent for reactive dyes comprises the following steps:
mixing 13.4 parts of deionized water and 0.5 part of an initiator (sodium sulfite and ammonium persulfate according to a molar ratio of 1;
adding 75 parts of 60 percent dimethyldiallylammonium chloride solution with the mass percentage concentration of 1/5 of the total mass into a reaction kettle under the nitrogen condition, stirring and heating to 75 ℃;
beginning the first dropwise adding (for 1.5 h) of the rest dimethyl diallyl ammonium chloride solution;
simultaneously secondly dropwise adding (for 0.7 h) 6 parts of acyloxy-containing cationic monomer (methacryloyloxyethyl dimethyl benzyl ammonium chloride) and 8 parts of cross-linking agent (diallyl amine);
simultaneously, dripping 1/5 of the total amount of the initiator solution (for 3 hours) for the third time, and heating to 90 ℃ after finishing dripping;
fourthly, dropwise adding 2/5 of the total amount of the initiator solution (the time is 1.5 h), keeping the temperature for 2-3h, and then heating to 100 ℃;
fifthly, dropwise adding (for 1.5 h) 2/5 of the total amount of the initiator solution, preserving the heat for 2-3h, cooling to 40 ℃, and discharging to obtain the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye.
And (3) determining the performance of the ternary polymerization efficient formaldehyde-free color fixing agent for the obtained reactive dye according to a national standard detection method to finally obtain: the charge requirement is 613 mu eq/L, the viscosity average molecular weight is 15.23 ten thousand, the sugar degree is 60.0 percent, and the dynamic viscosity is 5143mpa · s.
Example 2A preparation method of a ternary polymerization efficient formaldehyde-free color 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;
adding 72.5 parts of dimethyldiallylammonium chloride solution with the mass percentage concentration of 60 percent into a reaction kettle by 1/4 of the total mass under the condition of nitrogen, stirring and heating to 80 ℃;
beginning the first dropwise adding (for 3 h) of the rest dimethyl diallyl ammonium chloride solution;
simultaneously secondly dropwise adding (for 1 h) 5 parts of acyloxy-containing cationic monomer (methacryloyloxyethyl trimethyl ammonium chloride) and 10 parts of cross-linking agent (triallylamine);
simultaneously, thirdly dripping (for 4 hours) 1/5 of the total amount of the initiator solution, and heating to 95 ℃ after finishing dripping;
fourthly, dripping (for 2 hours) 2/5 of the total amount of the initiator solution, preserving the heat for 2-3 hours, and then heating to 105 ℃;
fifthly, dropwise adding 2/5 of the total amount of the initiator solution (for 2 hours), preserving heat for 2-3 hours, cooling to 40 ℃, and discharging to obtain the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye.
And (3) determining the performance of the ternary polymerization efficient formaldehyde-free color fixing agent for the obtained reactive dye according to a national standard detection method to finally obtain: the charge demand is 627 mu eq/L, the viscosity average molecular weight is 16.31 ten thousand, the sugar degree is 60.8 percent, and the dynamic viscosity is 11851mpa · 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;
under the condition of nitrogen, 73 parts of dimethyldiallylammonium chloride solution with the mass percentage concentration of 62 percent is added into a reaction kettle by 1/5 of the total mass, and the temperature is raised to 70 ℃ by stirring;
beginning the first dropwise adding (for 12 h) of the rest dimethyl diallyl ammonium chloride solution;
simultaneously, 4 parts of acyloxy-containing cationic monomer (acryloyloxyethyltrimethyl ammonium chloride) and 10 parts of crosslinking agent (N-methyldiallylamine) are added dropwise for 0.6 h;
simultaneously, thirdly dripping (the time is 2 hours) 1/5 of the total amount of the initiator solution, and heating to 85 ℃ after finishing dripping;
fourthly, dripping (for 1 h) 2/5 of the total amount of the initiator solution, preserving the heat for 2-3h, and then heating to 95 ℃;
fifthly, dropwise adding (for 1 h) 2/5 of the total amount of the initiator solution, preserving the heat for 2-3h, cooling to 40 ℃, and discharging to obtain the ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye.
And (3) determining the performance of the ternary polymerization efficient formaldehyde-free color fixing agent for the obtained reactive dye according to a national standard detection method to finally obtain: the required charge is 623 mu eq/L, the viscosity-average molecular weight is 20.85 ten thousand, the sugar degree is 59 percent, and the dynamic viscosity is 9027mpa & s.
Comparative example 1
The same as in example 1 except that the acyloxy group-containing cationic monomer was not added.
And (3) determining the performance of the obtained formaldehyde-free color fixing agent according to a national standard detection method to finally obtain: the charge requirement was 525. Mu. Eq/L, the viscosity average molecular weight was 15.32 ten thousand, the sugar degree was 61.3%, and the kinematic viscosity was 10235mpa · s.
Comparative example 2
The method is the same as example 1 except that the dimethyl diallyl ammonium chloride solution is completely added into the reaction kettle under the nitrogen condition, and then the temperature is raised by stirring; and the initiator solution is completely dripped during the third dripping.
And (3) determining the performance of the obtained formaldehyde-free color fixing agent according to a national standard detection method to finally obtain: the charge demand 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 9736mpa · s.
Test example 1
The high efficiency formaldehyde-free fixing agent prepared in examples 1-3 and comparative examples 1-2 was used to treat cotton fabric dyed with active scarlet cmcrea.red194 using a dip-fixing process with a fixing agent dosage of 1% (o.w.f), a pH of 5-7, a bath ratio of 1.
The performance of the cotton fabric after color fixation is detected according to a national standard detection method, and the main performance indexes are shown in table 1.
TABLE 1
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The ternary polymerization efficient formaldehyde-free color fixing agent for the reactive dye is characterized by being prepared from the following raw materials in parts by weight: 60-75 parts of dimethyl diallyl ammonium chloride solution, 1.0-7.0 parts of acyloxy-containing cationic monomer, 5.0-12.0 parts of cross-linking agent, 0.1-0.5 part of initiator and 10-25 parts of deionized water.
2. The efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye according to claim 1, characterized in that,
the mass percentage concentration of the dimethyl diallyl ammonium chloride solution is 50-65%.
3. The efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye according to claim 1, characterized in that,
the acyloxy-containing cationic monomer is at least one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl benzyl ammonium chloride and acryloyloxyethyl dimethyl benzyl ammonium chloride.
4. The efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye according to claim 1, characterized in that,
the crosslinking agent is at least one of diallylamine, triallylamine and N-methyldiallylamine.
5. The efficient ternary polymerization formaldehyde-free color fixing agent for the reactive dye according to claim 1, characterized in that,
the initiator is at least one of redox systems formed by sodium sulfite, ammonium persulfate, potassium persulfate and sodium persulfate.
6. The efficient ternary polymerization aldehyde-free color fixing agent for the reactive dye according to claim 1,
the negative charge demand 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.
7. The preparation method of the ternary polymerization efficient aldehyde-free color fixing agent for the reactive dye according to any one of claims 1 to 6, which is characterized by comprising the following steps:
mixing deionized water and an initiator to obtain an initiator solution;
adding 1/5-1/4 of the total mass of the dimethyl diallyl ammonium chloride solution into a reaction kettle under the condition of nitrogen, and stirring and heating to 70-80 ℃;
beginning the first drop of the remaining dimethyldiallylammonium chloride solution;
simultaneously, secondly dropping acyloxy-containing cationic monomer and cross-linking agent;
simultaneously, adding 1/5 of the total amount of the initiator solution dropwise, and heating to 85-95 ℃ after dropwise adding;
fourthly, dripping 2/5 of the total amount of the initiator solution, preserving the heat for 2-3h, and then heating to 95-105 ℃;
fifthly, dripping 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.
8. The production method according to claim 1,
the first dripping time is 1-3h; the time of the second dripping is 0.5-1h.
9. The production method according to claim 1,
the third dripping time is 2-4h; the fourth dripping time is 1-2h; the fifth dripping time is 1-2h.
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