CN116791383A - Cotton spinning cloth environment-friendly fixation method based on compound multi-cation waterborne polyurethane - Google Patents

Cotton spinning cloth environment-friendly fixation method based on compound multi-cation waterborne polyurethane Download PDF

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CN116791383A
CN116791383A CN202310199574.5A CN202310199574A CN116791383A CN 116791383 A CN116791383 A CN 116791383A CN 202310199574 A CN202310199574 A CN 202310199574A CN 116791383 A CN116791383 A CN 116791383A
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prepolymer
chain extender
reaction
glycol
diisocyanate
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汪峰
王世宇
刘栋良
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Zhejiang Daoyi New Material Co ltd
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Zhejiang Daoyi New Material Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271

Abstract

The invention discloses an environment-friendly fixation method for cotton spinning cloth based on complex waterborne cationic polyurethane, and belongs to the field of organic polymer fixation agents. The method is carried out according to the following process flow: the preparation method comprises the following steps of (1) a prepolymer prepolymerization reaction, (2) a small molecule chain extension reaction, (3) a cation chain extension reaction (4) an acid neutralization and emulsion emulsification reaction; the clear yellow polyurethane emulsion with the solid content of 12-15% and transparent appearance and no coalescence can be successfully obtained. According to the invention, polymerization inhibitors with different mass equivalent weights are explored and added in the prepolymerization part according to actual conditions, so that universality of the polymerization inhibitor on raw material requirements is expanded, and the polymerization inhibitor has a certain reference value for actual production; the chain extender and the cationic chain extender are compounded in various proportions in the chain extender part exploration, and the polyurethane color fixing scheme with high efficiency, environmental protection and durability is obtained in the initial step.

Description

Cotton spinning cloth environment-friendly fixation method based on compound multi-cation waterborne polyurethane
Technical Field
The invention belongs to the field of organic polymer color fixing agents, and relates to an environment-friendly cotton spinning cloth color fixing method based on compound multi-cation waterborne polyurethane.
Background
Cotton textiles are used as daily necessities of people and important industrial products, the improvement of product quality and the development of variety of products are always highly focused by industry, and especially, the environment-friendly dyeing and fixation scheme of fabrics becomes a research hot spot at present.
Although the existing various anionic dyes and reactive dyes can be used for stably dyeing cotton fabrics, the color fastness of dyed fabrics is poor due to the existence of the floating color which is formed on the surfaces of the fabrics by unavoidable hydrolysis and undyed dye molecules, and the stability of dye molecule bonds which are covalently combined with the cotton fabrics is easily influenced by various complex use environments, so that the fixation treatment needs to be continued after dyeing. The cationic color fixing agent reacts with the dye and the groups on the fiber to form covalent bonds, hydrogen bonds and the like, and forms a film on the surface of the cotton fabric to cut off the contact of the dye and the stains, so that various service performances such as the color fastness of the cotton fabric are improved.
In recent years, the textile market has more strict requirements on friction resistance, perspiration resistance, sun drying, ironing and other aspects of the cotton fabric after fixation, and after the ISO1400 standard is exported, the ecological influence and biodegradability of the use of the color fixing agent are more emphasized. Therefore, based on environmental protection and market demands, the color fixing scheme which is environment-friendly and has good application effect on cotton fabrics is very important.
The dicyandiamide formaldehyde cationic color fixing agent has good color fixing performance, but the formaldehyde released after finishing has serious influence on human bodies and environment; the polyamine color fixing agent forms a lake through cations in the structure and dye to obviously improve the color fastness, but contains more multilevel amine structures, and is easy to oxidize to cause the color change of fabrics; the cationic color fixing agent synthesized by epoxy chloropropane and amine effectively prevents color change, but reduces the color fastness to washing and perspiration.
Polyurethane (PU) is a polymer containing repeating urethane groups in the backbone. Wherein water can be used to replace organic solvent to form the water-soluble polyurethane of disperse emulsion system. The cationic aqueous polyurethane generally contains quaternary ammonium cationic groups on side chains, wherein the quaternary ammonium cationic groups react with hydroxyl groups and active acid dyes on the surfaces of cotton fabrics, and the stable fixation effect is obtained by utilizing anion-cation covalent bonding. The aqueous polyurethane can be used as a material, can realize excellent performances such as good film forming property, thermal stability and the like through optimal regulation of a formula, and provides support for developing a multifunctional fabric color fixing agent with strong practicability. Meanwhile, the method has small ecological influence and is environment-friendly, and has great development prospect.
Xie Yan et al in the "preparation and application of polyurethane" and in the text, reported the study of the preparation of cationic aqueous polyurethane fixing agents by using polytetrahydrofuran ether glycol (PTMG) and isophorone diisocyanate (IPDI) as main raw materials and N-methyldiethanolamine (N-MDEA) as cationic chain extender, discuss the effect of the addition of hydrophilic chain extender N-MDEA and different IPDI contents on the reaction, and test the emulsion particle size, thermogravimetric analysis, wet rubbing fastness, etc. of the product. The result shows that the cationic fixing agent can be well covalently bonded with anions on cellulose fibers, so that the dye is not easy to fall off. However, the research is only conducted on the MDEA single-component cationic chain extender, the comprehensive effect of the compound chain extender is not further explored, and the compound chain extender has a certain limitation.
Fan Shaoyu et al in the text of "synthesis and application of cationic aqueous polyurethane fixing agent", report that isophorone diisocyanate (IPDI) and polyether 1000 (PEG) are used as main raw materials, hydrophilic dimethylolbutyric acid (DMBA) is used as a chain extender, 2, 3-dibromosuccinic acid is used as a rear chain extender to prepare the aqueous polyurethane fixing agent, the influence of different R values, different chain extenders and the ratio of the rear chain extender on the reaction is discussed, and the product is tested on the rubbing fastness and the soaping fastness of the product applied to finishing after dyeing of cotton fabric reactive dyes. The result shows that the molecular chain of the cationic color fixing agent has higher cationic activity, and the color fixation of the reactive dye can be realized with higher efficiency. However, the key step of cation generation in the research, namely the affinity substitution reaction of triethylamine and 2, 3-dibromosuccinic acid, has great difference in reaction efficiency under different system conditions, reduces the universality of the method, and has non-negligible influence of reagents on human bodies and the environment.
Chinese patent 201010145722.8 (application) reports a preparation and application method of a blocked cationic waterborne polyurethane color fixing agent, wherein the preparation and application method is obtained through polyurethane prepolymer reaction, blocking reaction, acid neutralization and ionization reaction, and a method of inactivating isocyanate groups by blocking part after the prepolymer and releasing at high temperature during cotton fabric finishing is adopted. The color fixing method has the advantages that the color fixing method which is free of formaldehyde and high in color fixing efficiency is achieved, but the color fixing method has certain complexity in large-scale production operation, the solid content of the finally obtained emulsion is high, and the actual production cost is increased.
Disclosure of Invention
The invention aims to provide a novel environment-friendly color fixing agent synthesis method of compound multi-cation waterborne polyurethane, and the corresponding dyed cotton fabric is subjected to film coating finishing so as to obtain a good color fixing effect, and the application, particularly wet friction resistance, of the cotton fabric is improved.
The synthetic route of the invention can be divided into four steps: the first step is prepolymer prepolymerization, namely, prepolymerization is carried out by polyhydroxy polymer and isocyanate, and meanwhile, a proper amount of polymerization inhibitor is added to control the reaction rate and the reaction progress; the second step is a small molecule chain extension reaction, namely adding small molecule polyol into the system to further extend the molecular chain of the prepolymer to form a preliminary linear structure; and the third step is cationic chain extension reaction, namely, by continuously adding a cationic chain extender or a compound mixed cationic chain extender into the system, carrying cationic groups reacting with dyes and fibers, and further extending molecular chains and forming a three-dimensional structure. And the fourth step is acid neutralization and emulsion emulsification reaction, namely, the neutralization agent is added to improve the electrophilicity of the cationic groups, and water is used as a disperse phase to obtain an environment-friendly efficient color fixing agent emulsion system.
The invention discloses an environment-friendly fixation method for cotton spinning cloth based on compound multi-cation waterborne polyurethane, which comprises the following steps:
(1) Prepolymer prepolymerization reaction: vacuum dewatering polyhydroxy polymer monomer at 120deg.C under 0.04-0.08Mpa for 1.5h, waiting for cooling system temperature below 50deg.C, directly adding calculated amount of isocyanate monomer and polymerization inhibitor, wherein the polymerization inhibitor is pre-configured solution, and dewatering with polyhydroxy polymer. After the addition, the temperature of the system is regulated to 55-65 ℃ for reaction for 30 minutes, the temperature is continuously increased to 75 ℃ for reaction for 1 hour and 40 minutes. The NCO group content of the system is monitored by adopting an infrared spectrometry method, the reaction time is prolonged or shortened if necessary, and the NCO group mass residue in the step accounts for less than 3.43% of the prepolymer mass (%).
Wherein the polyhydroxy polymer specifically comprises: polyethylene glycol (PEG, molecular weight m=1450), polyethylene glycol (PEG, molecular weight m=800), polyethylene glycol (PEG, molecular weight m=500), tetrahydrofuran-propylene oxide copolyethers (P (eg\pg)), polybutadiene glycol (PBD), poly (1, 2-propanediol adipate) glycol (PPA), polytetrahydrofuran glycol (PTMG), poly (1, 4-butanediol adipate) glycol (PBA), castor oil, organosiloxane glycol; polyethylene glycol (PEG, molecular weight m=1450), polyethylene glycol (PEG, molecular weight m=800), polyethylene glycol (PEG, molecular weight m=500); polyethylene glycol (PEG), polytetrahydrofuran glycol (PTMG), polybutadiene glycol (PBD). The amount of hydroxyl groups was 1.83% of the total prepolymer mass.
Wherein the isocyanate monomer specifically comprises: 2, 4-toluene diisocyanate (2, 4-TDI), 2, 6-toluene diisocyanate (2, 6-TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1, 5-Naphthalene Diisocyanate (NDI), m-Xylylene Diisocyanate (XDI) Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), NCO groups account for 8.00% of the total prepolymer mass.
Wherein the polymerization inhibitor specifically comprises: 85% phosphoric acid, 20% hydrochloric acid, benzoyl chloride, phenylacetyl chloride, acetyl chloride and oxalyl chloride, and the polymerization inhibitor accounts for 0.04% -0.16% of the total prepolymer mass.
(2) Small molecule chain extension reaction: in the prepolymer system synthesized in the step, the calculated amount of the small molecular chain extender is continuously and directly added (if the small molecular chain extender is solid, the small molecular chain extender is directly poured into the prepolymer system without dissolution), wherein the dosage and the proportion of the small molecular chain extender are determined according to the actual product requirement, the total R value of the system and the proportion of the cationic chain extender, the system temperature is kept at 75 ℃ after the small molecular chain extender is added, the reaction is continuously carried out for 1h and 10min, the NCO group content of the system is monitored by adopting an infrared spectrometry, the reaction time is prolonged or shortened if necessary, and the NCO group mass residue in the step accounts for less than 2.73% of the mass (%) of the prepolymer.
Wherein the small molecule chain extender specifically comprises: 1, 4-butanediol (1, 4-BDO), 2-methyl-1, 3-propanediol, neopentyl glycol, 1, 6-hexanediol, and diethylpentanediol, and the amount of the small molecule chain extender is 1.4% of the total prepolymer mass.
(3) Cationic chain extension reaction: and cooling the synthesized prepolymer system to 50 ℃, and adding a proper amount of solvent to reduce the viscosity of the system according to actual conditions, wherein the added solvent needs to be removed by reduced pressure evaporation. After the viscosity of the system is obviously reduced, the calculated amount of the cationic chain extender or the compounded cationic chain extender is slowly injected into the system at a constant speed within 20-30 minutes through a constant pressure dropping funnel or an injector. After the addition is completed, the temperature of the system is raised to 50-55 ℃ and the reaction is kept for 2h. The viscosity is regulated by observing the viscosity change of the system and supplementing the solvent, and the infrared spectroscopy is adopted to monitor the change of the reaction NCO, so that the reaction time is prolonged or shortened if necessary. The NCO group mass residue in this step is in the range of < 1.36% of the prepolymer mass (%). The method comprises the steps of carrying out a first treatment on the surface of the
Wherein the cationic chain extender specifically comprises: diethanolamine, N-methyldiethanolamine, triisopropanolamine, dihydroxyisopropylaniline, dihydroxyisopropyl-p-toluidine, and the cationic chain extender represents 0.49% of the total prepolymer mass.
Wherein the compound cationic chain extender specifically comprises: a mixture of N-methyldiethanolamine and dihydroxyisopropylaniline; a mixture of N-methyldiethanolamine and dihydroxyisopropyl para-toluidine; triisopropanolamine, dihydroxyisopropylaniline, dihydroxyisopropyl para-toluidine, and the compounded cationic chain extender accounts for 0.49% of the total prepolymer mass.
Wherein the solvent specifically comprises: acetone, butanone, butyl acetate, N-dimethylformamide.
(4) Acid neutralization and emulsion emulsification reaction: and cooling the prepolymer subjected to cationic chain extension to room temperature, and calculating the dosage of the neutralizer according to the neutralization degree to ensure that the neutralization degree is 100-110%. Adding a neutralizing agent into the calculated amount of deionized water, rapidly adding the neutralizing agent into a prepolymer system under high-speed stirring, and continuously stirring and ionizing for 0.5 hour at room temperature to finally obtain a bright yellow transparent cationic aqueous polyurethane color fixing agent emulsion with the solid content of 12% -15%;
wherein the neutralizer specifically comprises: glacial acetic acid.
According to the invention, a polyurethane prepolymer with adjustable functions and high cationic group density and good fixation effect is obtained by adopting a method of two step chain extension after prepolymerization, and then the polyurethane fixation agent emulsion which is environment-friendly and free of organic solvents is obtained by deionized water self-emulsifying. The quaternary ammonium cations carried on the molecular chain of the color fixing agent in the color fixing process can be combined with acid dye and reactive dye molecules and can also be combined with hydroxyl on the surface of cotton textiles, so that a good color fixing effect is achieved by utilizing the covalent bond effect; meanwhile, the polyurethane main chain structure can form a lamellar or three-dimensional reticular film coating on the surface of the fabric, further restrict the hydrolysis of dye molecules and the like, and optimize the actual fixation effect under complex use environment; because of compounding a plurality of micromolecular chain extenders and cationic chain extenders, the intermolecular van der Waals force and hydrogen bond effect between groups on polyurethane molecular chains and the surface of the fabric are enhanced, and the fixation effect is further consolidated. The aqueous polyurethane color fixing agent synthesized by the method has the important characteristics that the aqueous polyurethane color fixing agent is used as an environment-friendly material with good color fixing effect, and has no organic solvent, formaldehyde and other irritant substances and harmful byproducts; the other important application characteristic is that the production and application series difficulty caused by the difference of the fine impurity content of industrial grade raw materials and laboratory medicines is focused on in combination with actual production, and the influence of the purity of the raw materials on the synthesis of the color fixing agent can be solved by adding a proper amount of polymerization inhibitor in the prepolymerization process, so that the production cost can be effectively reduced. In the practical cotton textile application finishing process, the conventional padding and baking operation can obtain the color fixing level equivalent to or even better than that of the commercial color fixing agent on key indexes such as dry friction resistance, wet friction resistance, soaping fastness, light fastness and the like.
Drawings
FIG. 1 is a color fixing performance of examples one, two, three and blank;
FIG. 2 is the fixing performance of examples four, five and commercially available fixing agents.
Detailed Description
The following examples illustrate the invention but in no way limit the scope of the invention.
Control example: 24.288g of polyethylene glycol (PEG-1450) with molecular weight M=1450 is weighed and added into a 250mL three-neck flask, 0.060g of 85% phosphoric acid is weighed and added into the three-neck flask, a stirring rod is inserted into the middle opening of the flask and is put into a mechanical stirring arm, a rubber plug with a thermometer is inserted into the side opening of the flask, the other side opening of the flask is connected with a vacuum circulating water pump, and a constant-temperature oil bath pot is put into the lower part of the flask. Starting an oil bath pot, starting a stirring pump and a vacuum pump after the polyethylene glycol is completely melted, and vacuum dewatering for 1.5h at 120 ℃ and a vacuum degree of 0.04-0.08 Mpa. Removing the vacuum water pump, cooling the system to below 50 ℃, adding 7.062g of 2, 4-toluene diisocyanate (TDI-80), stirring uniformly, heating to 55-65 ℃ for reaction for 30min, continuously heating to 75 ℃ for reaction for 1h and 40min, and maintaining the temperature. After monitoring the NCO group content of the system to be less than 3.43%, 1.150g of 1, 4-butanediol (1, 4-BDO) is weighed and added into the system, and the system is stirred uniformly, and the reaction is continued for 1h and 10min at 75 ℃. Monitoring the NCO group content of the system to be less than 2.73%, cooling the system to 55 ℃, adding 5.000g of acetone, uniformly stirring, sucking 0.510-g N-Methyldiethanolamine (MDEA) by a syringe after the viscosity of the system is reduced, slowly injecting the mixture into the system at a constant speed within 20-30 minutes, continuously heating the system to 60-62 ℃, and keeping the temperature for reaction for 2 hours. After 30min of reaction, 3.000g of acetone is added for viscosity reduction, and the reaction is continued. After monitoring the NCO group content of the system to be less than 1.36%, the system is cooled to 55 ℃, 0.320g of glacial acetic acid is weighed and poured into a mixed solution of 210.00g of deionized water and 5.8g of glacial acetic acid, and the mixture is evenly and rapidly poured into the system to be neutralized (the neutralization degree is 100%) and emulsified for 30min while being accelerated and stirred. Finally, the polyurethane emulsion with R value of 1.20 and solid content of 13.4 percent and transparent bright yellow is obtained.
Example 1: under the operation conditions of the comparative example, 1.150g of the small molecular chain extender 1, 4-butanediol is changed into 1.150g of 2-methyl-1, 3-propanediol, and the small molecular chain extender is added into the system, and other conditions are unchanged, so that the R value is 1.20, the solid content is 13.4 percent, and the polyurethane emulsion is transparent in bright yellow.
Example 2: under the operating conditions of the comparative examples, the theoretical R value of the prepolymer before emulsification was increased to 1.3 (by changing 7.062g of 2, 4-toluene diisocyanate to 7.650g of 2, 4-toluene diisocyanate), and the other conditions were unchanged, to give a bright yellow transparent polyurethane emulsion having an R value of 1.30 and a solids content of 13.6%.
Example 3: under the operating conditions of the comparative examples, the theoretical R value of the prepolymer before emulsification was increased to 1.4 (by changing 7.062g of 2, 4-toluene diisocyanate to 8.250g of 2, 4-toluene diisocyanate), and the other conditions were unchanged, to give a bright yellow transparent polyurethane emulsion having an R value of 1.40 and a solids content of 13.8%.
Example 4: under the operating conditions of the comparative example, the cationic chain extender 0.510, g N-methyldiethanolamine was replaced with 0.2365g of a mixture of diethanolamine and 0.2569g N-methyldiethanolamine (mass ratio of 1:1), and the other conditions were added to the system, leaving a clear yellow transparent polyurethane emulsion having an R value of 1.20 and a solids content of 13.4%.
Example 5: under the operation conditions of the comparative example, the cationic chain extension temperature is raised to 65-70 ℃, and other conditions are unchanged, so that the R value is 1.20, the solid content is 13.4%, and the polyurethane emulsion is transparent in bright yellow.
Color fixation effect test
Dosage of color fixing agent: shown in the following table; the pH value is 4-5; soaking temperature: 25 ℃; soaking time: 2min; bath ratio: 1:30; two-padding and two-rolling (rolling residual rate 80%), and the color fixing process flow comprises the following steps: dyeing, washing, fixing color, pre-drying, drying and testing; pre-drying: baking at 90 ℃ for 120 s: 140℃for 120s. The rubbing fastness is according to GB3920-2008 textile rubbing fastness test method; staining grade was rated on a gray sample card according to GB 251-1995.
The table above can show that the complex multi-cation aqueous polyurethane color fixing agent synthesized by the invention can treat the reddish cotton fabric under the same process condition, and the wet rubbing fastness of the treated cotton fabric can be improved by 1.5-2 grades compared with that of a control group (without color fixing treatment). The first, second and third examples have the color fixing performance shown in fig. 1, and the fourth and fifth examples have the color fixing performance shown in fig. 2, which show that the color fixing agent synthesized by the method has good color fixing capability and reaches a level even slightly better than that of the commercial color fixing agent.
Meanwhile, when tap water is used as a solvent to prepare working solution, the color fixing agent synthesized by the invention has good dispersion stability at the environmental temperature of 5-40 ℃, and has no gel or sediment, which is not possessed by the commercial color fixing agent. The color fixing agent synthesized by the invention has the remarkable advantages of environmental friendliness, simple synthesis method, strong functional adjustability and the like, and the comprehensive effect is superior to that of the latter.

Claims (3)

1. The environment-friendly fixation method for cotton spinning cloth based on the compound multi-cation waterborne polyurethane is characterized by comprising the following steps of:
(1) Prepolymer prepolymerization reaction: dehydrating the calculated amount of polyhydroxy polymer and polymerization inhibitor for 1.5 hours at 120 ℃ and 0.04-0.08Mpa vacuum degree, cooling to below 50 ℃, adding the calculated amount of isocyanate monomer, setting the reaction temperature to 55-65 ℃ for 30 minutes, continuously raising the temperature to 75 ℃ and keeping the temperature for 1 hour and 40 minutes. The NCO group mass residue in this step is in the range of < 3.43% of the prepolymer mass (%).
Wherein the polyhydroxy polymer comprises: polycarbonate diol and polyol, polyacrylate diol and polyol, polyether ester diol and polyol, amino-terminated polyether diol, castor oil and other bio-based polyols; wherein the hydroxyl functional group mass represents 1.83% of the total mass of the final prepolymer.
Wherein the polymerization inhibitor comprises: phosphoric acid and a pre-prepared solution, hydrochloric acid and a pre-prepared solution, aliphatic acid chloride, aromatic acid chloride, and the like. The polymerization inhibitor accounts for 0.04 to 0.16 percent of the total mass of the prepolymer.
Wherein the isocyanate monomer comprises: 2, 4-toluene diisocyanate (2, 4-TDI), 2, 6-toluene diisocyanate (2, 6-TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1, 5-Naphthalene Diisocyanate (NDI), m-Xylylene Diisocyanate (XDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) wherein NCO groups account for 8.00% of the total mass of the final prepolymer;
(2) Small molecule chain extension reaction: after the prepolymer is obtained by the first step of synthesis and the R value requirement is met, the calculated amount of chain extender is added, and the system temperature is kept at 75 ℃ for continuous reaction for 1 hour and 10 minutes. Wherein the selection of the chain extender determines the relevant types and proportions according to the actual product requirements, and the NCO group mass residue in the step accounts for less than 2.73% of the prepolymer mass (%).
Wherein the small molecule chain extender comprises: fatty diol, aromatic diol, fatty triol, alcohol amine diol, etc. account for 1.4% of the total mass of the prepolymer.
(3) Cationic chain extension reaction: and (3) cooling the synthesized prepolymer to 50 ℃, adding a proper amount of solvent according to the system viscosity requirement to reduce viscosity, adding a calculated amount of cationic chain extender, controlling the adding time to be 20-30 minutes, and after the cationic chain extender is completely added, raising the system temperature to 50-55 ℃ and keeping the reaction for 2 hours. Observing the viscosity change of the system and regulating the system by using a solvent, so that the mass ratio of the solvent before emulsification is about 18%. The change of the reaction NCO is monitored by an infrared spectrometry method, and the residual mass of NCO groups in the step accounts for less than 1.36% of the mass (%) of the prepolymer.
Wherein the solvent comprises: n, N-Dimethylformamide (DMF), butanone, acetone, ethyl acetate.
Wherein the cationic chain extender comprises: fatty tertiary amine, aromatic tertiary amine, etc. account for 0.49% of the total mass of the prepolymer.
(4) And (3) acid neutralization and emulsion emulsification reaction, namely cooling the prepolymer subjected to cationic chain extension to room temperature, and calculating the dosage of a neutralizing agent according to the neutralization degree to obtain the neutralization degree of 100-110%. Adding the neutralizer into the calculated amount of deionized water, rapidly adding the prepolymer system under high-speed stirring, and continuously stirring and ionizing for 0.5 hour at room temperature to finally obtain the transparent cation aqueous polyurethane color fixing agent emulsion with bright yellow appearance and 12-15% of solid content.
Wherein the neutralizing agent comprises: glacial acetic acid, dilute hydrochloric acid and dimethyl sulfate.
2. The environment-friendly fixation method for cotton fabric of the compound multi-cation waterborne polyurethane, which is characterized by comprising the following steps:
wherein the polyhydroxy polymer is: polyethylene glycol (PEG, molecular weight m=1450), polyethylene glycol (PEG, molecular weight m=800), polyethylene glycol (PEG, molecular weight m=500), polyethylene oxide glycol (PEG), tetrahydrofuran-propylene oxide copolyethers (P (eg\pg)), polybutadiene glycol (PBD), poly (1, 2-propanediol adipate) glycol (PPA), polytetrahydrofuran glycol (PTMG), poly (1, 4-butanediol adipate) glycol (PBA), castor oil, organosiloxane glycol.
Wherein the isocyanate monomer is as follows: 2, 4-toluene diisocyanate (2, 4-TDI), 2, 6-toluene diisocyanate (2, 6-TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1, 5-Naphthalene Diisocyanate (NDI), m-Xylylene Diisocyanate (XDI) Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI).
Wherein the polymerization inhibitor specifically comprises: 85% phosphoric acid, 20% hydrochloric acid, benzoyl chloride, phenylacetyl chloride, acetyl chloride and oxalyl chloride.
Wherein the small molecule chain extender specifically comprises: 1, 4-butanediol (1, 4-BDO), 2-methyl-1, 3-propanediol, neopentyl glycol, 1, 6-hexanediol, diethylpentanediol.
Wherein the cationic chain extender specifically comprises: diethanolamine, N-methyldiethanolamine, triisopropanolamine, dihydroxyisopropylaniline, dihydroxyisopropyl-p-toluidine.
Wherein the solvent specifically comprises: acetone, butanone, butyl acetate, N-dimethylformamide.
Wherein the neutralizer specifically comprises: glacial acetic acid.
3. The cotton spinning cloth environment-friendly fixation method based on the compound multi-cation waterborne polyurethane, which is characterized by comprising the following steps of:
wherein the polyhydroxy polymer is: polyethylene glycol (PEG, molecular weight m=1450), polyethylene glycol (PEG, molecular weight m=800), a mixture of polyethylene glycols (PEG, molecular weight m=500), a mixture of polyethylene oxide glycol (PEG), polytetrahydrofuran glycol (PTMG), polybutadiene glycol (PBD).
Wherein the cationic chain extender is: a mixture of N-methyldiethanolamine and dihydroxyisopropylaniline; a mixture of N-methyldiethanolamine and dihydroxyisopropyl para-toluidine; triisopropanolamine, dihydroxyisopropylaniline, and dihydroxyisopropyl-p-toluidine.
CN202310199574.5A 2023-03-04 2023-03-04 Cotton spinning cloth environment-friendly fixation method based on compound multi-cation waterborne polyurethane Pending CN116791383A (en)

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