CN101768884B - Multi-quaternary ammonium group cation type polyurethane color fixing agent and preparation method thereof - Google Patents

Abstract

The invention discloses a multi-quaternary ammonium group cation type polyurethane color fixing agent (see structural formula (I)), and a preparation method thereof. The preparation method comprises the following steps of: weighing 1.3-153.2 parts by weight of diisocyanate a, 3.7-365 parts by weight of diisocyanate b, 4.5-584 parts by weight of polyatomic alcohol, 0.02-1 part by weight of catalyst, 2-100 parts by weight of polyhydroxy tertiary amine compounds, 2-236 parts by weight of alkylating reagents, 1-38 parts by weight of sealers, 5-80 parts by weight of organic solvents a, 5-100 partsby weight of organic solvents b, 10-50 parts by weight of organic solvents c, 0.1-5 parts by weight of acidizing reagents and 20-800 parts by weight of deionized water in weight ratio; sequentially preparing a multi-quaternary ammonium group chain extender and a polyurethane prepolymer for chain-extension reaction, sealing reaction, removing solvent and emulsifying to obtain the color fixing agent. The color fixing agent prepared by the preparation method reduces the water solubility of dyes and improves the color fastness of the dyes, and fabrics have soft hand feeling after being fixed. In the formula, X is a sealing group, Y is a diisocyanate main group, Z is polyurethane soft section, R and R'are alkyl groups or hydroxyl groups, and n is equal to 1-15.

Description

Polyquaternary ammonium cationic polyurethane color fixing agent and preparation method thereof

technical field

The invention belongs to the technical field of textile dyeing and finishing, and in particular relates to a polyquaternary ammonium cationic polyurethane color-fixing agent, and also relates to a preparation method of the color-fixing agent.

Background technique

After the textile is dyed with anionic dyes such as direct dyes and acid dyes, its wet color fastness is poor. Even if the fabric dyed with reactive dyes, its wet rubbing fastness is not enough to meet the quality requirements, so it generally has to go through Color-fixing treatment can meet various color fastness standards for wearing and using. Color-fixing agents such as color-fixing agent Y, color-fixing agent M, and cross-linking agent DE have been banned because they contain free formaldehyde. At present, most of the formaldehyde-free color-fixing agents used are polyamine polymer compounds, such as the color-fixing agent DM-2518 of Guangzhou Demei Chemical Co., Ltd., and the formaldehyde-free color-fixing agent TF-233 of Zhejiang Chuanhua Chemical Group Co., Ltd. etc. These color-fixing agents have good color-fixing effects when applied to pure cotton, polyester-cotton and polyester-viscose fabrics with direct dyes and reactive dyes, but the color-fixing effects on darker fabrics, silk, wool and other fabrics are very general. .

Contents of the invention

The purpose of the present invention is to provide a polyquaternary ammonium cationic polyurethane color-fixing agent, which solves the problem that the existing color-fixing agent has poor color-fixing effects on darker-colored fabrics and fabrics such as silk and wool.

Another object of the present invention is to provide a method for preparing the above-mentioned polyquaternary ammonium-based cationic polyurethane color-fixing agent.

The technical scheme adopted in the present invention is, a kind of multi-quaternary ammonium cationic polyurethane color fixing agent, its molecular formula is:

In the formula, X—blocking group; Y—diisocyanate main group; Z—polyurethane soft segment;

R, R'—alkyl or alkoxyl; n=1-15.

Another technical solution adopted in the present invention is a method for preparing the above-mentioned color-fixing agent, which is specifically implemented according to the following steps:

Step 1: According to the weight ratio, weigh 1.3-153.2 parts of diisocyanate a, 3.7-365 parts of diisocyanate b, 4.5-584 parts of polypolyol, 0.02-1 part of catalyst, 2-100 parts of polyhydroxy tertiary amine compounds, 2-236 parts of alkylating reagent, 1-38 parts of blocking agent, 5-80 parts of organic solvent a, 5-100 parts of organic solvent b, 10-50 parts of organic solvent c, 10-100 parts of organic solvent d, 0.1- 5 parts of acidifying reagent and 20-800 parts of deionized water;

Step 2: Preparation of multiple quaternary ammonium-based chain extenders:

Add the polyhydroxy tertiary amine compound and organic solvent a weighed in step 1 into the dry reactor, and mix to obtain a mixed solution, add the diisocyanate a weighed in step 1 dropwise to the mixed solution, React under the conditions for 1-2 hours, then heat up to 50-100°C, dropwise add the alkylating agent weighed in step 1, and reflux for 2-5 hours to obtain a polyquaternary ammonium-based chain extender;

Preparation of polyurethane prepolymer:

In the dry reactor, add the diisocyanate b and the organic solvent b weighed in step 1 to obtain a mixed solution, add dropwise the polypolyol weighed in step 1 in the mixed solution, and then add the catalyst weighed in step 1, at 50 React at -90°C for 2-4 hours to obtain a polyurethane prepolymer;

Step 3: Chain extension reaction

Add the polyquaternary ammonium-based chain extender obtained in step 2 to the polyurethane prepolymer, add the organic solvent c weighed in step 1, and react at 40-90°C for 1.5-2 hours to obtain a polyurea with an isocyanate group as the terminal group. Polyurethane polymer;

Step 4: Blocking the reaction

Cool down the polyurethane polymer obtained in step 3 to 0-10°C, add the organic solvent d weighed in step 1, and then add the blocking agent weighed in step 1, and conduct a blocking reaction for 1-2 hours to obtain a polyurethane polymer with terminal block Lotion;

Step 5: Solvent removal and emulsification

Distill the polyurethane polymer emulsion obtained in step 4 under reduced pressure, remove the organic solvent, adjust the pH value to 5.5-6.5 with the acidifying agent weighed in step 1, then add the deionized water weighed in step 1, emulsify 0.5-6.5 After 1 hour, an emulsion-like polyquaternary ammonium cationic polyurethane color fixing agent was obtained.

The present invention is also characterized in that,

The diisocyanate is toluene diisocyanate, xylylene diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, methylcyclohexyl One of diisocyanate, dicyclohexylmethane diisocyanate, tetramethylbenzene dimethylene diisocyanate or 1,6-hexamethylene diisocyanate.

Among them, the polypolyol adopts polyester polyol or polyether polyol, and the polyester polyol adopts polyethylene adipate diol, polydiethylene adipate diol, polyadipic acid -One of 1,4-butanediol ester diol, polyethylene adipate-propylene glycol ester diol or polycarbonate-1,6-hexanediol ester diol, or a mixture of two or more thereof ; Polyether polyol adopts one of oxyethylene diol, polyoxypropylene diol or polytetrahydrofuran diol, or a mixture of two or more thereof.

The catalyst is one of dibutyltin dilaurate, stannous octoate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate or tetraisobutyl titanate.

The polyhydroxy tertiary amine compounds are triethanolamine, N-methyldiethanolamine, N-isopropyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine or 3-dimethylamino-1, One of 2-propanediol, or a mixture of two or more of them.

The alkylating agent is dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, pentadiene One of dimethyl ester, benzyl chloride, benzyl bromide, alkyl bromide or alkyl iodide.

The blocking agent is N-methylmethylamine, N-ethylethylamine, N-isopropylpropylamine, N-methylethylamine, N-ethylmethylamine, N-methylpropylamine, N-methyl One of aniline, N-ethylaniline, sodium bisulfite, methyl ethyl ketone oxime, phenol or caprolactam.

The organic solvents are ethyl acetate, butyl acetate, acetone, butanone, 1,2-dichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, isopropanol, n-propanol , anhydrous ethanol or tetrahydrofuran.

Wherein the acidifying reagent adopts glacial acetic acid.

The beneficial effect of the invention is that the color fixing agent is used for the post-dyeing treatment of textiles, can improve the washing fastness and dry and wet rubbing color fastness of various anionic dyes, and keep the fabric soft to the touch.

Detailed ways

The present invention will be described in detail below in combination with specific embodiments.

The multi-quaternary ammonium cationic polyurethane color fixing agent of the present invention, its representative chemical structural formula is:

In the formula,

X—blocking group;

Y—diisocyanate main group;

Z—polyurethane soft segment;

R, R'—alkyl, alkyl hydroxyl, etc.;

n=1-15.

The preparation method of multi-quaternary ammonium cationic polyurethane color fixing agent of the present invention, specifically implement according to the following steps:

Step 1: According to the weight ratio, weigh 1.3-153.2 parts of diisocyanate a, 3.7-365 parts of diisocyanate b, 4.5-584 parts of polypolyol, 0.02-1 part of catalyst, 2-100 parts of polyhydroxy tertiary amine compounds, 2-236 parts of alkylating reagent, 1-38 parts of blocking agent, 5-80 parts of organic solvent a, 5-100 parts of organic solvent b, 10-50 parts of organic solvent c, 10-100 parts of organic solvent d, 0.1- 5 parts of acidifying reagent and 20-800 parts of deionized water;

The diisocyanates are toluene diisocyanate (TDI), xylylene diisocyanate (XDI), naphthalene-1,5-diisocyanate (NDI), diphenylmethane-4,4'-diisocyanate (MDI) , isophorone diisocyanate (IPDI), methylcyclohexyl diisocyanate (HTDI), dicyclohexylmethane diisocyanate (HMDI), tetramethylbenzene dimethylene diisocyanate (TMXDI) or 1,6-hexyl One of diisocyanate (HDI);

Among them, the polypolyol adopts polyester polyol or polyether polyol, and the polyester polyol adopts polyethylene adipate diol (PEA), polyethylene adipate diol (PDA) ), poly(1,4-butylene adipate) diol (PBA), polyethylene adipate-propylene glycol ester diol or polycarbonate-1,6-hexanediol diol (PHC) One or a mixture of two or more of them; polyether polyols use one or a mixture of two or more of oxyethylene glycol (PEG), polypropylene oxide glycol (PPG) or polytetrahydrofuran glycol (PTMG) ;

The catalysts are dibutyltin dilaurate (DBTDL), stannous octoate, lead octoate (24% Pb), cobalt octoate (6% Co), iron octoate (6% Fe), zinc naphthenate (14.5% Zn) Or one of tetraisobutyl titanate;

Wherein polyhydroxy tertiary amine compound adopts triethanolamine (TEA), N-methyldiethanolamine (MDEA), N-isopropyldiethanolamine, N-ethyldiethanolamine (EDEA), N-butyldiethanolamine ( BDEA) or 3-dimethylamino-1,2-propanediol or a mixture of two or more;

The alkylating agent is dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, pentadiene One of dimethyl ester, benzyl chloride, benzyl bromide, alkyl bromide or alkyl iodide;

The blocking agent wherein adopts N-methylmethylamine (dimethylamine), N-ethylethylamine (diethylamine), N-isopropylpropylamine, N-methylethylamine, N-ethylmethylamine, One of N-methylpropylamine, N-methylaniline, N-ethylaniline, sodium bisulfite, methyl ethyl ketone oxime, phenol or caprolactam;

Wherein the organic solvent adopts ethyl acetate, butyl acetate, acetone, butanone, 1,2-dichloroethane, N-methylpyrrolidone, N, N-dimethylformamide (DMF), isopropanol, One of n-propanol, absolute ethanol or tetrahydrofuran;

Wherein the acidifying reagent adopts glacial acetic acid.

Step 2: Preparation of multiple quaternary ammonium-based chain extenders:

Add the polyhydroxy tertiary amine compound and organic solvent a weighed in step 1 into the dry reactor, and mix to obtain a mixed solution, add the diisocyanate a weighed in step 1 dropwise to the mixed solution, React under the conditions for 1-2 hours, then heat up to 50-100°C, dropwise add the alkylating agent weighed in step 1, and reflux for 2-5 hours to obtain a polyquaternary ammonium-based chain extender;

Preparation of polyurethane prepolymer:

Add the diisocyanate b and organic solvent b weighed in step 1 into the dry reactor to obtain a mixed solution, add the polypolyol weighed in step 1 dropwise to the mixed solution with a dropping funnel, and then add the weighed polyol in step 1 Catalyst, reacting at 50-90°C for 2-4 hours to obtain a polyurethane prepolymer;

Step 3: Chain extension reaction

Add the polyquaternary ammonium-based chain extender obtained in step 2 to the polyurethane prepolymer, add the organic solvent c weighed in step 1, and react at 40-90°C for 1.5-2 hours to obtain a polyurea with an isocyanate group as the terminal group. Polyurethane polymer;

Step 4: Blocking the reaction

Cool down the polyurethane polymer obtained in step 3 to 0-10°C, add the organic solvent d weighed in step 1, and then add the blocking agent weighed in step 1, and conduct a blocking reaction for 1-2 hours to obtain a polyurethane polymer with terminal block Lotion;

Step 5: Solvent removal and emulsification

Distill the polyurethane polymer emulsion obtained in step 4 under reduced pressure, remove the organic solvent, adjust the pH value to 5.5-6.5 with the acidifying agent weighed in step 1, then add the deionized water weighed in step 1, and emulsify with high speed Machine emulsification for 0.5-1 hour to obtain emulsion polyquaternary ammonium cationic polyurethane color fixing agent.

The polyquaternary ammonium cationic polyurethane color-fixing agent of the present invention introduces an appropriate number of quaternary ammonium cationic groups on the polyurethane macromolecular chain, and they can combine with the dye anion groups on the fiber to reduce the water solubility of the dye; at the same time, Under certain conditions, the blocking group on the color fixing agent molecule can also form covalent bonds with the hydroxyl, amino, carboxyl hydroxyl, etc. on the fiber and dye molecules after unblocking, thereby improving the color fastness of the dye, especially wet treatment color fastness. Due to the excellent elasticity and flexibility of polyurethane polymers, compared with other types of color fixing agents, the fabric feels soft after treatment.

Example 1

(1) Preparation of multiple quaternary ammonium-based chain extenders

Add 100 parts of triethanolamine (TEA) and 60 parts of N-methylpyrrolidone into the dry reactor, then add 153.2 parts of MDI, and keep the temperature at 10°C for 2 hours. Gradually raise the temperature to 95°C, add 236.4 parts of hexadecane iodide, and reflux for 2 hours to obtain a polyquaternary ammonium-based chain extender. Cool down to room temperature, flush into nitrogen and seal for later use.

Preparation of Polyurethane Prepolymer

The mixture of 24 parts of PEG600 and 60 parts of PPG1500 was distilled under reduced pressure at 100°C for 2 hours, and after cooling down to 50°C, 25 parts of acetone was added, sealed for later use. Add 41 parts of MDI into the dry reactor, fill it with nitrogen for protection, drop the mixture of the above two polyether diols into the dropping funnel, add 0.03 parts of DBTDL, control the temperature at 55 ° C, and keep it warm for 2 hours to prepare Obtain polyurethane prepolymer;

(2) chain extension reaction

Add 35 parts of acetone to the polyurethane prepolymer prepared in (1) above, then dropwise add the polyquaternary ammonium-based chain extender prepared in (1) above, control the temperature to 70° C., and reflux for 2 hours under nitrogen protection.

(3) Blocking reaction

The temperature of the polymer obtained after the above reaction was lowered to 5° C., 35 parts of absolute ethanol was added, and 2 parts of N-methylmethylamine were added to block the reaction for 1.5 hours.

(4) Removal of solvent

The solvent is distilled off under reduced pressure to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent.

(5) emulsification

Add 5 parts of glacial acetic acid to adjust the pH to 5.5, add 600 parts of deionized water, and emulsify on a high-speed emulsifier for 0.8 hours to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.

Example 2

(1) Preparation of multiple quaternary ammonium-based chain extenders

Add 2 parts of N-ethyldiethanolamine (MDEA) and 5 parts of N-methylpyrrolidone into the dry reactor, then add 1.3 parts of HDI, and keep the temperature at 15°C for 2 hours. Gradually raise the temperature to 90°C, add 2.1 parts of benzyl chloride, and reflux for 2 hours to obtain a polyquaternary ammonium-based chain extender. Cool down to room temperature, flush into nitrogen and seal it for later use, and obtain a polyquaternary ammonium-based chain extender.

Preparation of Polyurethane Prepolymer

Distill 4.5 parts of PEG600 under reduced pressure at 100°C for 2 hours, add 5 parts of acetone after cooling down to 55°C, and seal it for later use. Add 3.7 parts of IPDI to the dry reactor, fill it with nitrogen for protection, add the above-mentioned PEG600 dropwise into the dropping funnel, add 0.2 parts of stannous octoate, control the temperature at 50°C, and keep it warm for 2 hours to prepare a polyurethane prepolymer;

(2) chain extension reaction

Add 10 parts of acetone to the polyurethane prepolymer prepared in (1) above, then dropwise add the polyquaternary ammonium-based chain extender prepared in (1) above, control the temperature at 75° C., and reflux for 2 hours under nitrogen protection.

(3) Blocking reaction

Cool the polymer obtained after the above reaction to 0°C, add 10 parts of isopropanol, and then add 1 part of sodium bisulfite, and block the reaction for 1 hour.

(4) Removal of solvent

The solvent is distilled off under reduced pressure to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent.

(5) emulsification

Add 0.1 part of glacial acetic acid to adjust the pH to 6.5, add 20 parts of deionized water, and emulsify on a high-speed emulsifier for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.

Example 3

(1) Preparation of multiple quaternary ammonium-based chain extenders

Add 10.7 parts of 3-dimethylamino-1,2-propanediol, 13.4 parts of triethanolamine (TEA), 66 parts of N-methyldiethanolamine (MDEA) and 80 parts of N-methylpyrrolidone into the dry reactor , and then add 91 parts of MDI and keep the temperature at 10°C for 2 hours. Gradually raise the temperature to 100°C, add 125 parts of benzyl bromide, and reflux for 2 hours to obtain a polyquaternary ammonium-based chain extender. Cool down to room temperature, flush into nitrogen and seal for later use.

Preparation of Polyurethane Prepolymer

Distill 584 parts of PEG800 under reduced pressure at 100°C for 2 hours, add 100 parts of acetone after cooling down to 60°C, and seal it for future use. Add 365 parts of MDI into the dry reactor, fill it with nitrogen for protection, add the above-mentioned PEG800 dropwise into the dropping funnel, add 1 part of stannous octoate, control the temperature at 60°C, and keep it warm for 2.5 hours to prepare a polyurethane prepolymer;

(2) chain extension reaction

Add 50 parts of acetone to the polyurethane prepolymer prepared in (1) above, then dropwise add the polyquaternary ammonium-based chain extender prepared in (1) above, control the temperature at 90° C., and reflux for 2 hours under nitrogen protection.

(3) Blocking reaction

The temperature of the polymer obtained after the above reaction was lowered to 10° C., 100 parts of absolute ethanol was added, and 38 parts of sodium bisulfite were added to block the reaction for 2 hours.

(4) Removal of solvent

The solvent is distilled off under reduced pressure to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent.

(5) emulsification

Add 4.5 parts of glacial acetic acid to adjust the pH to 6, and add 800 parts of deionized water to emulsify under high-speed shear force for 0.5 hours to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.

Example 4

(1) Preparation of multiple quaternary ammonium-based chain extenders

Add 42.9 parts of N-methyldiethanolamine (MDEA), 53.7 parts of triethanolamine (TEA) and 80 parts of N-methylpyrrolidone into the dry reactor, then add 94.0 parts of TDI, and keep the temperature at 3°C for 2 hours. Gradually raise the temperature to 60°C, add 61.5 parts of benzyl bromide, and reflux for 2 hours to obtain a polyquaternary ammonium-based chain extender. Cool down to room temperature, flush into nitrogen and seal for later use.

Preparation of Polyurethane Prepolymer

Distill 180 parts of PTMG1000 under reduced pressure at 100°C for 2 hours, add 30 parts of acetone after cooling down to 55°C, and seal it for future use. Add 90 parts of MDI into the dry reactor, fill it with nitrogen for protection, add polyether glycol dropwise into the dropping funnel, add 0.1 part of lead octoate (24% Pb), control the temperature at 90 ° C, and keep the reaction for 4 hours. Prepare polyurethane prepolymer;

(2) chain extension reaction

Add 60 parts of acetone to the polyurethane prepolymer prepared in (1) above, then dropwise add the polyquaternary ammonium-based chain extender prepared in (1) above, control the temperature to 40°C, and reflux for 1.5 hours under nitrogen protection.

(3) Blocking reaction

The temperature of the polymer obtained after the above reaction was lowered to 5° C., 55 parts of isopropanol was added, and 9.87 parts of N-ethylethylamine were added to block the reaction for 1.5 hours.

(4) Removal of solvent

The solvent is distilled off under reduced pressure to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent.

(5) emulsification

Add 4.8 parts of glacial acetic acid to adjust the pH to 6, and add 596 parts of deionized water to emulsify under high-speed shear force for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.

Example 5

(1) Preparation of multiple quaternary ammonium-based chain extenders

Add 42.8 parts of 3-dimethylamino-1,2-propanediol and 60 parts of N-methylpyrrolidone into the dry reactor, then add 23.4 parts of TDI, and keep the temperature at 8°C for 1 hour. Gradually raise the temperature to 50°C, add 110 parts of hexadecane bromide, and reflux for 5 hours to obtain a polyquaternary ammonium-based chain extender. Cool down to room temperature, flush into nitrogen and seal for later use.

Preparation of Polyurethane Prepolymer

The mixture of 60 parts of PTMG800, 36 parts of PEG800 and 90 parts of PPG1500 was distilled under reduced pressure at 100°C for 2 hours, and after cooling down to 55°C, 30 parts of acetone was added, sealed for later use. Add 80 parts of IPDI into the dry reactor, fill it with nitrogen for protection, drop the mixture of three polyether diols into the dropping funnel, add 0.6 parts of DBTDL, control the temperature at 60°C, and keep it warm for 2.5 hours to obtain Polyurethane prepolymer;

(2) chain extension reaction

Add 35 parts of acetone to the polyurethane prepolymer prepared in (1) above, then dropwise add the polyquaternary ammonium-based chain extender prepared in (1) above, control the temperature at 80° C., and reflux for 2 hours under nitrogen protection.

(3) Blocking reaction

The temperature of the polymer obtained after the above reaction was lowered to 5° C., 50 parts of isopropanol was added, and 9.87 parts of N-ethylethylamine were added to block the reaction for 1.5 hours.

(4) Removal of solvent

The solvent is distilled off under reduced pressure to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent.

(5) emulsification

Add 2.1 parts of glacial acetic acid to adjust the pH to 6.5, and add 450 parts of deionized water to emulsify under high-speed shear force for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.

Example 6

(1) Preparation of multiple quaternary ammonium-based chain extenders

Add 26.9 parts of triethanolamine (TEA) and 80 parts of N-methylpyrrolidone into the dry reactor, then add 15.1 parts of HDI, and keep the temperature at 10°C for 1.5 hours. Gradually raise the temperature to 75°C, add 22.8 parts of dimethyl sulfate, and reflux for 3 hours to obtain a polyquaternary ammonium-based chain extender. Cool down to room temperature, flush into nitrogen and seal for later use.

Preparation of Polyurethane Prepolymer

Distill 180 parts of PTMG1500 and 48 parts of PPG800 under reduced pressure at 100°C for 2 hours, add 35 parts of acetone after cooling down to 65°C, and seal it for future use. Add 80 parts of IPDI into the dry reactor, fill it with nitrogen for protection, drop the mixture of two polyether diols into the dropping funnel, control the temperature at 65°C, and keep it warm for 2.5 hours to prepare a polyurethane prepolymer;

(2) chain extension reaction

Add 35 parts of acetone to the polyurethane prepolymer prepared in (1) above, then dropwise add the polyquaternary ammonium-based chain extender prepared in (1) above, control the temperature to 70°C, and reflux for 2 hours under nitrogen protection.

(3) Blocking reaction

Cool the polymer obtained after the above reaction to 5°C, add 50 parts of isopropanol, then add 6.6 parts of N-ethylethylamine and 6.8 parts of N-methylpropylamine, and block the reaction for 1.5 hours.

(4) Removal of solvent

The solvent is distilled off under reduced pressure to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent.

(5) emulsification

Add 1.3 parts of glacial acetic acid to adjust the pH to 6, and add 360 parts of deionized water to emulsify under high-speed shear force for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.

The comparative result of table 1 the present invention and other fixing agents

Color Fixing Agent Varieties Dry/wet rubbing fastness (grade) Color fastness to soaping (grade) feel formaldehyde Fixing agent DM-2518 3-4/2-3 3-4 harder none Fixing agent TF-233 3-4/2-3 3-4 harder none Embodiment 1 of the present invention 4/3-4 4 soft none Embodiment 2 of the present invention 4/3-4 4 soft none Embodiment 3 of the present invention 4/3 4 soft none

Embodiment 4 of the present invention 4/3-4 4 soft none Embodiment 5 of the present invention 4/3-4 4 soft none Embodiment 6 of the present invention 4/3-4 4 soft none

Note: 1. Dry and wet rubbing fastness: GB/T3920-1997

2. Soaping fastness: GB/T3921.1-1997

3. Formaldehyde: GB/T2912.1-1998. The first part of water extraction method

As can be seen from Table 1, the polyquaternary ammonium cationic polyurethane color-fixing agent of the present invention, due to the softness and elasticity of the polyurethane soft segment, the fabric after finishing is soft to the touch, and the dry and wet rubbing fastness and washing fastness of the dyed fabric are all excellent.

Claims (2)

1. A multi-quaternary ammonium cationic polyurethane color fixing agent is characterized in that its molecular formula is:

In the formula, X-blocking group; Y-diisocyanate main group; Z-polyurethane soft segment; R, R'-alkyl or alkoxyl; n=1-15. 2. a method for preparing the color-fixing agent according to claim 1, is characterized in that, specifically implement according to the following steps: Step 1: Preparation of multiple quaternary ammonium-based chain extenders Add 100 parts of triethanolamine and 60 parts of N-methylpyrrolidone into the dry reactor, then add 153.2 parts of diphenylmethane-4,4'-diisocyanate, keep the temperature at 10°C for 2 hours, and gradually raise the temperature to 95 ℃, add 236.4 parts of hexadecane iodide, and reflux for 2 hours to obtain a polyquaternary ammonium-based chain extender, cool down to room temperature, flush into nitrogen and seal it for later use; Preparation of Polyurethane Prepolymer Distill the mixture of 24 parts of ethylene oxide diol 600 and 60 parts of polyoxypropylene diol 1500 under reduced pressure at 100°C for 2 hours, add 25 parts of acetone after cooling down to 50°C, seal it for later use, and add 41 Parts of diphenylmethane-4,4'-diisocyanate, filled with nitrogen for protection, drop the mixture of the above two polyether glycols with a dropping funnel, add 0.03 parts of dibutyltin dilaurate, control the temperature at 55 °C, heat preservation reaction for 2 hours to obtain a polyurethane prepolymer; Step 2: Chain extension reaction Add 35 parts of acetone to the polyurethane prepolymer prepared in the above step 1, then dropwise add the polyquaternary ammonium-based chain extender prepared in the above step 1, control the temperature to 70°C, and reflux for 2 hours under nitrogen protection; Step 3: Blocking the reaction Cool the polymer obtained after the above step 2 reaction to 5°C, add 35 parts of absolute ethanol, then add 2 parts of N-methylmethylamine, and block the reaction for 1.5 hours; Step 4: Solvent removal The solvent is distilled off under reduced pressure to obtain the polyquaternary ammonium cationic polyurethane color-fixing agent; Step 5: Emulsify Add 5 parts of glacial acetic acid to adjust the pH to 5.5, and add 600 parts of deionized water, and emulsify on a high-speed emulsifier for 0.8 hours to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion; or, Step 1: Preparation of multiple quaternary ammonium-based chain extenders Add 2 parts of N-ethyldiethanolamine and 5 parts of N-methylpyrrolidone into the dry reactor, then add 1.3 parts of 1,6-hexamethylene diisocyanate, keep the temperature at 15°C for 2 hours, and gradually raise the temperature to 90°C , add 2.1 parts of benzyl chloride, reflux for 2 hours to obtain a polyquaternary ammonium chain extender, cool down to room temperature, flush into nitrogen and seal it for later use, and obtain a polyquaternary ammonium chain extender; Preparation of Polyurethane Prepolymer Distill 4.5 parts of ethylene oxide glycol 600 under reduced pressure at 100°C for 2 hours, add 5 parts of acetone after cooling down to 55°C, seal it for later use, add 3.7 parts of isophorone diisocyanate into the dry reactor, and fill it with nitrogen For protection, add the above-mentioned ethylene oxide glycol 600 dropwise with a dropping funnel, add 0.2 parts of stannous octoate, control the temperature at 50°C, and keep it warm for 2 hours to prepare a polyurethane prepolymer; Step 2: Chain extension reaction Add 10 parts of acetone to the polyurethane prepolymer prepared in the above step 1, then dropwise add the polyquaternary ammonium-based chain extender prepared in the above step 1, control the temperature at 75°C, and reflux for 2 hours under nitrogen protection; Step 3: Blocking the reaction Cool the polymer obtained after the above step 2 reaction to 0°C, add 10 parts of isopropanol, then add 1 part of sodium bisulfite, and block the reaction for 1 hour; Step 4: Solvent removal The solvent is distilled off under reduced pressure to obtain the polyquaternary ammonium cationic polyurethane color-fixing agent; Step 5: Emulsify Add 0.1 part of glacial acetic acid to adjust the pH to 6.5, add 20 parts of deionized water, and emulsify on a high-speed emulsifier for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion; or, Step 1: Preparation of multiple quaternary ammonium-based chain extenders 10.7 parts of 3-dimethylamino-1,2-propanediol, 13.4 parts of triethanolamine, 66 parts of N-methyldiethanolamine and 80 parts of N-methylpyrrolidone were added to the dry reactor, and then 91 parts of di Phenylmethane-4,4'-diisocyanate, keep the temperature at 10°C for 2 hours, gradually raise the temperature to 100°C, add 125 parts of benzyl bromide, and reflux for 2 hours to obtain a polyquaternary ammonium chain extender. Into the nitrogen seal standby; Preparation of Polyurethane Prepolymer Distill 584 parts of ethylene oxide glycol 800 under reduced pressure at 100°C for 2 hours, add 100 parts of acetone after cooling down to 60°C, seal it for later use, and add 365 parts of diphenylmethane-4,4'- Diisocyanate, fill it with nitrogen for protection, add the above-mentioned ethylene oxide glycol 800 dropwise with a dropping funnel, add 1 part of stannous octoate, control the temperature at 60 ° C, and keep it warm for 2.5 hours to prepare a polyurethane prepolymer; Step 2: Chain extension reaction Add 50 parts of acetone to the polyurethane prepolymer prepared in the above step 1, then drop the above For the polyquaternary ammonium-based chain extender prepared in step 1, the temperature is controlled at 90° C., and the reaction is refluxed under nitrogen protection for 2 hours; Step 3: Blocking the reaction Cool the polymer obtained after the above step 2 reaction to 10°C, add 100 parts of absolute ethanol, then add 38 parts of sodium bisulfite, and block the reaction for 2 hours; Step 4: Solvent removal The solvent is distilled off under reduced pressure to obtain the polyquaternary ammonium cationic polyurethane color-fixing agent; Step 5: Emulsify Add 4.5 parts of glacial acetic acid to adjust the pH to 6, and add 800 parts of deionized water to emulsify under high-speed shear force for 0.5 hours to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion; or, Step 1: Preparation of multiple quaternary ammonium-based chain extenders Add 42.9 parts of N-methyldiethanolamine, 53.7 parts of triethanolamine and 80 parts of N-methylpyrrolidone into the dry reactor, then add 94.0 parts of toluene diisocyanate, keep the temperature at 3 ° C for 2 hours, and gradually raise the temperature to 60 ℃, add 61.5 parts of benzyl bromide, and reflux for 2 hours to obtain a polyquaternary ammonium-based chain extender, cool down to room temperature, flush into nitrogen and seal it for later use; Preparation of Polyurethane Prepolymer Distill 180 parts of polytetrahydrofuran diol 1000 under reduced pressure at 100°C for 2 hours, add 30 parts of acetone after cooling down to 55°C, seal it for later use, and add 90 parts of diphenylmethane-4,4'- Diisocyanate is filled with nitrogen for protection, polyether diol is added dropwise with a dropping funnel, 0.1 part of lead octoate is added, the temperature is controlled at 90 ° C, and the heat preservation reaction is carried out for 4 hours to obtain a polyurethane prepolymer; Step 2: Chain extension reaction Add 60 parts of acetone to the polyurethane prepolymer prepared in the above step 1, then dropwise add the polyquaternary ammonium-based chain extender prepared in the above step 1, control the temperature at 40°C, and reflux for 1.5 hours under nitrogen protection; Step 3: Blocking the reaction Cool the polymer obtained after the above step 2 reaction to 5°C, add 55 parts of isopropanol, then add 9.87 parts of N-ethylethylamine, and block the reaction for 1.5 hours; Step 4: Solvent removal The solvent is distilled off under reduced pressure to obtain the polyquaternary ammonium cationic polyurethane color-fixing agent; Step 5: Emulsify Add 4.8 parts of glacial acetic acid to adjust the pH to 6, and add 596 parts of deionized water to emulsify under high-speed shear force for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion; or, Step 1: Preparation of multiple quaternary ammonium-based chain extenders Add 42.8 parts of 3-dimethylamino-1,2-propanediol and 60 parts of N-methylpyrrolidone into the dry reactor, then add 23.4 parts of toluene diisocyanate, keep the temperature at 8°C for 1 hour, and gradually heat up to At 50°C, add 110 parts of hexadecane bromide and reflux for 5 hours to obtain a polyquaternary ammonium-based chain extender, cool down to room temperature, flush into nitrogen and seal it for later use; Preparation of Polyurethane Prepolymer A mixture of 60 parts of polytetrahydrofuran diol 800, 36 parts of ethylene oxide diol 800 and 90 parts of polyoxypropylene diol 1500 was distilled under reduced pressure at 100°C for 2 hours, and after cooling down to 55°C, 30 parts of acetone were added, sealed for later use, Add 80 parts of isophorone diisocyanate in the dry reactor, fill with nitrogen to protect, drop the mixture of three kinds of polyether diols with dropping funnel, add 0.6 part of dibutyltin dilaurate, control the temperature at 60°C, heat preservation reaction for 2.5 hours to prepare polyurethane prepolymer; Step 2: Chain extension reaction Add 35 parts of acetone to the polyurethane prepolymer prepared in the above step 1, then dropwise add the polyquaternary ammonium-based chain extender prepared in the above step 1, control the temperature at 80°C, and reflux for 2 hours under nitrogen protection; Step 3: Blocking the reaction Cool the polymer obtained after the above step 2 reaction to 5°C, add 50 parts of isopropanol, and then add 9.87 parts of N-ethylethylamine, and block the reaction for 1.5 hours; Step 4: Solvent removal The solvent is distilled off under reduced pressure to obtain the polyquaternary ammonium cationic polyurethane color-fixing agent; Step 5: Emulsify Add 2.1 parts of glacial acetic acid to adjust the pH to 6.5, and add 450 parts of deionized water to emulsify under high-speed shear force for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion; or, Step 1: Preparation of multiple quaternary ammonium-based chain extenders Add 26.9 parts of triethanolamine and 80 parts of N-methylpyrrolidone into the dry reactor, then add 15.1 parts of 1,6-hexamethylene diisocyanate, keep the temperature at 10°C for 1.5 hours, gradually raise the temperature to 75°C, and add 22.8 parts Dimethyl sulfate was refluxed for 3 hours to obtain a polyquaternary ammonium-based chain extender, which was cooled to room temperature, flushed into nitrogen and sealed for subsequent use; Preparation of Polyurethane Prepolymer Distill 180 parts of polytetrahydrofuran diol 1500 and 48 parts of polyoxypropylene diol 800 under reduced pressure at 100°C for 2 hours, add 35 parts of acetone after cooling down to 65°C, seal it for later use, and add 80 parts of iso Phortone diisocyanate, filled with nitrogen for protection, dropwise adding the mixture of two polyether diols with a dropping funnel, controlling the temperature at 65°C, and keeping the temperature for 2.5 hours to prepare a polyurethane prepolymer; Step 2: Chain extension reaction Add 35 parts of acetone to the polyurethane prepolymer prepared in the above step 1, then dropwise add the polyquaternary ammonium-based chain extender prepared in the above step 1, control the temperature at 70°C, and reflux for 2 hours under nitrogen protection; Step 3: Blocking the reaction Cool the polymer obtained after the above step 2 reaction to 5°C, add 50 parts of isopropanol, then add 6.6 parts of N-ethylethylamine, 6.8 parts of N-methylpropylamine, and block the reaction for 1.5 hours; Step 4: Solvent removal The solvent is distilled off under reduced pressure to obtain the polyquaternary ammonium cationic polyurethane color-fixing agent; Step 5: Emulsify Add 1.3 parts of glacial acetic acid to adjust the pH to 6, and add 360 parts of deionized water to emulsify under high-speed shear force for 1 hour to obtain a polyquaternary ammonium cationic polyurethane color-fixing agent emulsion.