CN102604002B - Preparation method of multifunctional waterborne polyurethane and quaternary ammonium polymer - Google Patents

Abstract

The invention discloses a preparation method of a multifunctional waterborne polyurethane-quaternary ammonium salt polymer. The method of the present invention comprises the following steps: firstly, polypolyol, diol and polyisocyanate are mixed, reacted for a certain period of time under the action of a quaternary ammonium salt catalyst, and then sequentially add metered first hydrophilic chain extender and second chain extender , Hydroxyl-containing unsaturated monomers and tertiary amines are reacted to prepare a prepolymer solution; water-based polyurethane prepolymers and quaternary ammonium salts containing unsaturated groups are mixed in a certain molar ratio, and the oxidation-reduction initiator effect Under the copolymerization reaction, the multifunctional water-based polyurethane-quaternary ammonium salt polymer is obtained. The product prepared by the preparation method of the multifunctional water-based polyurethane-quaternary ammonium salt polymer of the present invention can increase the comprehensive properties such as color fastness, softness and air permeability of dyed fabrics or fibers, and is non-toxic or low-toxic and environmentally friendly .

Description

Preparation method of multifunctional waterborne polyurethane-quaternary ammonium salt polymer

technical field

The invention belongs to the technical field of chemistry and chemical engineering, and in particular relates to a preparation method of a multifunctional water-based polyurethane-quaternary ammonium salt polymer.

Background technique

During the dyeing process of fabric or fiber, a certain chemical bond or intermolecular force can be formed between the dye and the fabric or fiber, and brighter colors can be dyed, but because most of the dye molecules contain soluble groups, the wet fastness is not good , so as to stain the fabric or fibres. In order to avoid the appearance of these phenomena, color fixing agents are mainly used for color fixing treatment. Fixing agent has the ability to improve the fixation rate of dyes on fabrics or fibers and the fastness to wet treatment during the dyeing process, which is of great significance for improving product quality, reducing production costs, and reducing pollution. However, a considerable part of the color-fixing agent contains formaldehyde, and a certain amount of formaldehyde will remain after the dyed fabric or fiber is finished, which will affect the health of the human body and limit its application.

Since the 1960s, solvent-based polyurethane has been widely used. However, organic solvents are volatile and cause air pollution. With the gradual enhancement of human environmental protection awareness and my country's accession to the WTO, the internationalization of products is becoming more and more demanding. development of water-based materials. Water-based polyurethane uses water as the basic medium. First, the molecular structure contains a large number of active groups such as isocyanate groups and hydroxyl groups. The combination of inter-strength and other forces can improve the color fastness of washing and abrasion resistance; second, the raw materials and products do not contain formaldehyde and volatiles, which are non-polluting, non-toxic, and easy to operate and process; third, it has good film-forming properties And elasticity, can give fabrics or fibers good air permeability, softness, fullness and other characteristics. The practice of water-based polyurethane in the textile printing and dyeing industry shows that its application research in the textile industry has potential prospects, but there are still defects such as low wet fastness in terms of color fixing and other functions. Developing towards the direction of non-toxic, high performance and multifunctionality, it is a current research hotspot to strengthen the design of functional molecules of waterborne polyurethane and introduce molecular groups with special functions into the main chain of the molecule by various methods to improve the comprehensive performance of waterborne polyurethane.

Contents of the invention

The purpose of the present invention is to provide a multifunctional water-based polyurethane-quaternary ammonium salt for the problems of poor color fastness, poor softness and air permeability, toxicity, and environmental pollution of dyed fabrics or fibers in the prior art. Polymer preparation methods.

The inventive method comprises the following steps:

(1) Preparation of polyurethane prepolymer solution: add 7-12 parts of dibasic alcohol, 80-90 parts of polypolyol and 0.5-1 part of quaternary ammonium salt catalyst into the reaction vessel for mixing, dehydration treatment under vacuum, and then Add 45-55 parts of polyisocyanate dropwise, heat up the reaction under the protection of inert gas, and then add 4-8 parts of the first hydrophilic chain extender, 5-8 parts of the second chain extender, 3-5 parts Saturated monomers are reacted, then 3-6 parts of tertiary amines are added to react, and the temperature is lowered to obtain a polyurethane prepolymer solution;

(2) Preparation of initiator solution: 1-2 parts of oxidation-reduction initiator are dissolved in 320-360 parts of water to obtain initiator solution;

(3) Preparation of multifunctional water-based polyurethane-quaternary ammonium salt polymer: take 150-180 parts of the polyurethane prepolymer solution prepared in step (1), heat up, add 30-60 parts of quaternary ammonium salt for mixing, add 130-200 parts of the initiator solution described in step (2) react, then add the remaining initiator solution of step (2) gained, cool down after the insulation reaction, multi-functional water-based polyurethane-quaternary ammonium salt polymer;

The above parts are all parts by mass.

More specifically, the heating temperature in step (1) is 65-80°C; the cooling temperature in step (1) is below 50°C. The heating temperature in step (3) is 70-85°C; the cooling temperature in step (3) is below 50°C.

The inert gas in step (1) is one or a mixture of two or more of nitrogen, helium and argon.

The glycol described in step (1) is one or both of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol The mixture of any proportion; The quaternary ammonium salt catalyst described in the step (1) and the quaternary ammonium salt described in the step (3) are dimethyl allyl p-benzoyl benzyl ammonium bromide and dimethyl diallyl One or two mixtures of ammonium chloride in any proportion.

The polyisocyanate described in step (1) is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate and dicyclohexylmethane diisocyanate in one or more than two mixtures in arbitrary proportions; the polypolyol described in the step (1) is that the molecular weight is 600,800,1000,1500,2000g/mol One of polyethylene glycol and polypropylene glycol with a molecular weight of 800, 1000, 1500, and 2000 g/mol or a mixture of two or more in any proportion.

The first hydrophilic chain extender described in step (1) is one or a mixture of two or more in arbitrary proportions in dimethylol propionic acid, methylol butyric acid, tartaric acid and dimethylol butyric acid half ester ; The second chain extender described in step (1) is one or a mixture of two or more in any proportion in diethylene triamine, triethylene tetramine, propylene diamine and isophorone diamine.

The hydroxyl group-containing unsaturated monomer in step (1) is one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate or a mixture of two or more in any proportion.

The tertiary amine in the step (1) is one or a mixture of two or more of trimethylamine, triethylamine and N-methyldiethanolamine in any proportion.

The oxidation-reduction initiator described in step (2) is one or more of ammonium persulfate-sodium bisulfite, ammonium persulfate-sodium sulfite, sodium persulfate-sodium bisulfite and potassium persulfate-sodium sulfite Mixtures in any proportion.

The multifunctional water-based polyurethane-quaternary ammonium salt polymer of the present invention utilizes molecular structure design and adjusts the ratio of soft and hard segments in the polymer molecular chain, effectively improving the softness and stiffness of dyed fabrics or fibers; using quaternary ammonium The chemical bond or intermolecular force between the base and the group in the dye or fiber molecule can effectively increase the dye uptake rate of the dye on the fiber; use its film-forming property to further improve the fixation rate of the dye on the fabric or fiber. Because the multifunctional water-based polyurethane-quaternary ammonium polymer molecular chain contains a large number of active groups such as hydroxyl, amino, and quaternary ammonium salts, it is easy to combine with hydroxyl, amino, etc. in fibers and dyes through chemical bonds or intermolecular forces. , to firmly combine the dye and fiber molecules; at the same time, the water-based polyurethane-quaternary ammonium polymer with corresponding soft and hard segments in its molecules evenly adheres to the surface of the fiber to form a film, which not only firmly coats the dye on the fabric or On the fiber, it also improves the softness and other functions of the fabric or fiber, and effectively improves the dyeing fastness and wearability of the dyed fabric or fiber.

Compared with the prior art, the present invention has the following beneficial effects:

The multifunctional water-based polyurethane-quaternary ammonium salt polymer of the present invention can realize high performances such as color fixation, softness, air permeability and stiffness of dyed fabrics or fibers; Polyurethane-quaternary ammonium salt polymer, the performance indicators of its dyed fabrics or fibers are significantly improved, such as dry and wet rubbing fastness and other performance indicators can reach above grade 4, with increased softness and good air permeability; multifunctional water-based Polyurethane-quaternary ammonium salt polymer uses water as a solvent without the release of harmful solvents. At the same time, by controlling the reaction conditions, the content of free monomeric diisocyanate in the product is reduced, making the product low or non-toxic and environmentally friendly. product.

Detailed ways

The present invention will be further described in detail below in conjunction with specific experimental examples.

Example 1:

After adding 7 parts of ethylene glycol, 80 parts of polyethylene glycol 600 and 1 part of dimethylallyl p-benzoylbenzyl ammonium bromide into the reaction vessel and mixing them, after dehydration treatment in a vacuum state, in nitrogen Under protection, heat up to 80°C, add 45 parts of 2,4-toluene diisocyanate dropwise for 1.5 hours, then add 4 parts of dimethylolpropionic acid for chain extension reaction for 0.5 hours, and 5 parts of diethylenetriamine for chain extension reaction for 0.5 hours 1. React 5 parts of hydroxyethyl acrylate for 1 hour, then add 6 parts of trimethylamine to react for 0.5 hours, and cool down to 30°C to prepare a polyurethane prepolymer solution;

1 part of ammonium persulfate-sodium bisulfite is dissolved in 320 parts of water to obtain initiator solution;

Take 150 parts of polyurethane prepolymer solution, heat up to 85°C, add 30 parts of dimethylallyl-p-benzoylbenzyl ammonium bromide for mixing, then drop 160 parts of initiator solution in 10 minutes to react for 0.5 hours, Then add the remaining initiator solution within 2 hours, keep the temperature for 2 hours, then cool down to 40°C, multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 2:

After adding 8 parts of ethylene glycol, 81 parts of polyethylene glycol 800 and 0.5 part of dimethylallyl p-benzoylbenzyl ammonium bromide into the reaction vessel and mixing them, after dehydration treatment in a vacuum state, in nitrogen Warm up to 65°C under protection, add 56 parts of 2,4-toluene diisocyanate dropwise for 2 hours, then add 5 parts of dimethylol propionic acid for chain extension reaction for 0.5 hours, 8 parts of diethylenetriamine for chain extension reaction for 0.5 hours, React 3 parts of hydroxyethyl acrylate for 2 hours, then add 5 parts of trimethylamine to react for 0.5 hours, and cool down to 30°C to prepare a polyurethane prepolymer solution;

2 parts of ammonium persulfate-sodium bisulfite are dissolved in 330 parts of water to obtain initiator solution;

Take 160 parts of polyurethane prepolymer solution, raise the temperature to 80°C, add 40 parts of dimethylallyl-p-benzoylbenzyl ammonium bromide and mix them, then add 160 parts of initiator solution dropwise within 10 minutes and react for 0.5h. Then add the remaining initiator solution within 2 hours, keep the temperature for 2 hours, then cool down to 40°C, multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 3:

After adding 9 parts of 1,3-propanediol, 82 parts of polyethylene glycol 1000 and 0.6 part of dimethylallyl p-benzoylbenzyl ammonium bromide into the reaction vessel and mixing them, after dehydration treatment under vacuum, Under the protection of nitrogen, the temperature was raised to 70°C, and 47 parts of 2,6-toluene diisocyanate was added dropwise to react for 2 hours, followed by adding 6 parts of dimethylol butyric acid for chain extension reaction for 1 hour, 6 parts of triethylenetetramine for chain extension reaction for 1 hour, 4 parts of hydroxypropyl acrylate were reacted for 1 hour, then 3 parts of trimethylamine were added for reaction for 1 hour, and the temperature was lowered to 50°C to prepare a polyurethane prepolymer solution;

1.5 parts of ammonium persulfate-sodium sulfite are dissolved in 340 parts of water to obtain initiator solution;

Take 170 parts of polyurethane prepolymer solution, raise the temperature to 75°C, add 50 parts of dimethyl diallyl ammonium chloride for mixing, drop 170 parts of initiator solution in 10 minutes to react for 0.5 hours, and then add in 2 hours After the remaining initiator solution was kept for 3 hours, the temperature was lowered to 50°C to form a multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 4:

After adding 10 parts of 1,3-propanediol, 83 parts of polyethylene glycol 1500 and 0.7 part of dimethylallyl-p-benzoylbenzyl ammonium bromide into the reaction vessel and mixing them, after dehydration treatment in a vacuum state, Under the protection of helium, the temperature was raised to 75°C, and 48 parts of 2,6-toluene diisocyanate was added dropwise for 2 hours, followed by 7 parts of dimethylolbutyric acid for chain extension reaction for 0.6 hours, and 7 parts of triethylenetetramine for chain extension reaction. 0.6h, 3 parts of hydroxypropyl acrylate reacted for 2h, then added 4 parts of triethylamine to react for 1h, cooled to 30°C to prepare polyurethane prepolymer solution;

1.5 parts of ammonium persulfate-sodium sulfite are dissolved in 350 parts of water to obtain initiator solution;

Take 180 parts of polyurethane prepolymer solution, raise the temperature to 85°C, add 60 parts of dimethylallyl-p-benzoylbenzyl ammonium bromide and mix them, then add 170 parts of initiator solution dropwise within 5 minutes to react for 0.5h. Then add the remaining initiator solution within 2 hours, keep the temperature for 1 hour, then cool down to 40°C, multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 5:

After adding 11 parts of 1,4-butanediol, 50 parts of Polyethylene Glycol 2000, 30 parts of Polypropylene Glycol 2000 and 0.8 part of dimethyl allyl p-benzoyl benzyl ammonium bromide in the reaction vessel and mix, in After dehydration treatment in a vacuum state, the temperature was raised to 80°C under the protection of helium, and 49 parts of isophorone diisocyanate was added dropwise to react for 2 hours, followed by adding 8 parts of tartaric acid for chain extension reaction for 0.5 h, and 4 parts of propylenediamine for chain extension React for 0.5h, react with 5 parts of hydroxyethyl methacrylate for 1h, then add 3 parts of triethylamine to react for 0.5h, cool down to 40°C, and prepare a polyurethane prepolymer solution;

1 part of sodium persulfate-sodium bisulfite is dissolved in 360 parts of water to obtain initiator solution;

Take 150 parts of polyurethane prepolymer solution, raise the temperature to 70°C, add 30 parts of dimethyl diallyl ammonium chloride for mixing, add 160 parts of initiator solution dropwise within 20 minutes to react for 0.5 hours, and then add within 2 hours The remaining initiator solution was kept for 2 hours, and then cooled to 40°C to form a multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 6:

Add 12 parts of 1,5-pentanediol, 84 parts of polypropylene glycol 800, and 0.9 parts of dimethyl diallyl ammonium chloride into the reaction vessel, mix them, and carry out dehydration treatment under vacuum. Then, under the protection of helium, Raise the temperature to 70°C, add 50 parts of hexamethylene diisocyanate dropwise for 2 hours, then add 8 parts of tartaric acid for chain extension reaction for 0.5 hours, 6 parts of isophorone diamine for chain extension reaction of 0.5 hours, 5 parts of methacrylic acid hydroxyl Ethyl ester was reacted for 1 h, then 4 parts of triethylamine was added to react for 0.5 h, and the temperature was lowered to 40°C to obtain a polyurethane prepolymer solution;

2 parts of sodium persulfate-sodium bisulfite are dissolved in 320 parts of water to obtain initiator solution;

Take 160 parts of polyurethane prepolymer solution, heat up to 85°C, add 30 parts of dimethyl diallyl ammonium chloride for mixing, drop 160 parts of initiator solution in 20 minutes to react for 0.5 hours, and then add in 2 hours The remaining initiator solution was kept for 2 hours, and then cooled to 40°C to form a multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 7:

Add 7 parts of 1,5-pentanediol, 85 parts of polypropylene glycol 1000 and 1 part of dimethyl diallyl ammonium chloride into the reaction vessel and mix them, then carry out dehydration treatment under vacuum, and then under the protection of argon Raise the temperature to 75°C, add 51 parts of xylylene diisocyanate dropwise for 1.5 hours, then add 7 parts of dimethylol butyrate half ester for chain extension reaction for 0.5 hours, and 7 parts of isophorone diamine for chain extension reaction 0.5h, 5 parts of hydroxyethyl methacrylate were reacted for 1h, then 5 parts of N-methyldiethanolamine was added to react for 0.5h, and the temperature was lowered to 30°C to prepare a polyurethane prepolymer solution;

1.5 parts of potassium persulfate-sodium sulfite are dissolved in 330 parts of water to obtain initiator solution;

Take 160 parts of polyurethane prepolymer solution, raise the temperature to 85°C, add 40 parts of dimethylallyl-p-benzoylbenzyl ammonium bromide and mix them, then add 160 parts of initiator solution dropwise within 10 minutes to react for 0.5h. Then add the remaining initiator solution within 2 hours, keep the temperature for 2 hours, then cool down to 40°C, multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 8:

After adding 8 parts of 1,3-propanediol, 88 parts of polypropylene glycol 1000 and 0.5 part of dimethyl diallyl ammonium chloride into the reaction vessel and mixing them, after dehydration treatment in a vacuum state, the temperature was raised to At 80°C, add 53 parts of 1,5-naphthalene diisocyanate dropwise for 1.5 hours, then add 8 parts of dimethylol butyrate half ester for chain extension reaction for 0.5 hours, 8 parts of propylenediamine for chain extension reaction for 0.5 hours, and 4 parts React hydroxypropyl methacrylate for 1 hour, then add 6 parts of N-methyldiethanolamine to react for 0.5 hour, and cool down to 30°C to prepare a polyurethane prepolymer solution;

1.5 parts of potassium persulfate-sodium sulfite are dissolved in 340 parts of water to obtain initiator solution;

Take 170 parts of polyurethane prepolymer solution, heat up to 80°C, add 50 parts of dimethyl diallyl ammonium chloride for mixing, drop 160 parts of initiator solution in 10 minutes to react for 0.5 hours, and then add in 2 hours The remaining initiator solution was kept for 2 hours, and then cooled to 40°C to form a multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Example 9:

After adding 9 parts of 1,3-propanediol, 90 parts of polypropylene glycol 2000 and 0.8 part of dimethyl diallyl ammonium chloride into the reaction vessel and mixing them, after dehydration treatment in a vacuum state, the temperature was raised to At 80°C, add 55 parts of dicyclohexylmethane diisocyanate dropwise for 1.5 hours, then add 5 parts of dimethylol butyrate half ester for chain extension reaction for 0.5 hours, 8 parts of isophorone diamine for chain extension reaction for 0.5 hours, React 3 parts of hydroxypropyl methacrylate for 1 hour, then add 3 parts of N-methyldiethanolamine to react for 0.5 hours, and lower the temperature to 30°C to prepare a polyurethane prepolymer solution;

2 parts of potassium persulfate-sodium sulfite are dissolved in 360 parts of water to obtain initiator solution;

Take 180 parts of polyurethane prepolymer solution, heat up to 85°C, add 60 parts of dimethylallyl-p-benzoylbenzyl ammonium bromide and mix them, then add 160 parts of initiator solution dropwise within 10 minutes to react for 0.5h. Then add the remaining initiator solution within 2 hours, keep the temperature for 2 hours, then cool down to 40°C, multi-functional water-based polyurethane-quaternary ammonium salt polymer.

Application example:

Under the condition that other conditions remain unchanged, after the pure cotton fabric is treated with 2% of the multifunctional waterborne polyurethane-quaternary ammonium salt polymer of the present invention, the test results are shown in Table 1.

Table 1 List of multifunctional waterborne polyurethane-quaternary ammonium salt polymers applied to pure cotton fabrics

The above is only a preferred embodiment of the present invention, so all equivalent changes or modifications made according to the process principle described in the scope of the patent application of the present invention are included in the scope of the patent application of the present invention.

Claims (9)

1. the preparation method of a multifunctional type aqueous polyurethane-QAS polymer is characterized in that may further comprise the steps:

⑴ the preparation of polyurethane prepolymer solution: after dibasic alcohol, 80-90 part polyvalent alcohol and 0.5-1 part quaternary ammonium salt catalyst adding reaction vessel of 7-12 part is mixed, processed under vacuum state, drip again the polyisocyanates of 45-55 part, temperature reaction under protection of inert gas, after add successively 4-8 part the first hydrophilic chain extender, 5-8 part the second chainextender, the reaction of 3-5 part hydroxyl unsaturated monomer, then add 3-6 part reactive tertiary amine, cooling makes polyurethane prepolymer solution;

⑵ the preparation of initiator solution: the oxidation-reduction initiator of 1-2 part is dissolved in 320-360 part water obtains initiator solution;

⑶ the preparation of multifunctional type aqueous polyurethane-QAS polymer: get the prepared polyurethane prepolymer solution of 150-180 part step ⑴, heat up, after adding 30-60 part quaternary ammonium salt is mixed, add the described initiator solution reaction of 160-180 part step ⑵, the residue initiator solution of rear adding step ⑵ gained, lower the temperature after the insulation reaction, get multifunctional type aqueous polyurethane-QAS polymer;

Above umber all is mass fractions;

Wherein, quaternary ammonium salt described in quaternary ammonium salt catalyst described in the step ⑴ and the step ⑶ is that dimethyl-allyl is to the mixture of one or both arbitrary proportions in benzoyl benzyl brometo de amonio and the dimethyl diallyl ammonium chloride; The unsaturated monomer of hydroxyl described in the step ⑴ is the mixture of one or more arbitrary proportions in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and the Rocryl 410; Polyvalent alcohol described in the step ⑴ is that molecular weight is 600,800,1000,1500, the polyoxyethylene glycol of 2000g/mol and molecular weight are 800,1000,1500, the mixture of one or more arbitrary proportions in the polypropylene glycol of 2000g/mol.

2. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: the temperature of intensification described in the step ⑴ is 65-80 ℃; The temperature of cooling described in the step ⑴ is below 50 ℃.

3. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: the temperature of intensification described in the step ⑶ is 70-85 ℃; The temperature of cooling described in the step ⑶ is below 50 ℃.

4. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1 is characterized in that: rare gas element described in the step ⑴ is one or more mixture in nitrogen, helium and the argon gas.

5. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: dibasic alcohol described in the step ⑴ is ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1, the mixture of one or more arbitrary proportions in 5-pentanediol and 1, the 6-hexylene glycol.

6. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: polyisocyanates described in the step ⑴ is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1, the mixture of one or more arbitrary proportions in 5-naphthalene diisocyanate and the dicyclohexyl methane diisocyanate.

7. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: the first hydrophilic chain extender described in the step ⑴ is the mixture of one or more arbitrary proportions in dimethylol propionic acid, dimethylolpropionic acid, tartrate and the dimethylolpropionic acid half ester; The second chainextender described in the step ⑴ is the mixture of one or more arbitrary proportions in diethylenetriamine, triethylene tetramine, propylene diamine and the isophorone diamine.

8. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: tertiary amine described in the step ⑴ is the mixture of one or more arbitrary proportions in Trimethylamine 99, triethylamine and the N methyldiethanol amine.

9. the preparation method of multifunctional type aqueous polyurethane-QAS polymer according to claim 1, it is characterized in that: oxidation-reduction initiator described in the step ⑵ is the mixture of one or more arbitrary proportions in ammonium persulfate-sodium bisulfite, ammonium persulphate-S-WAT, Sodium Persulfate-sodium bisulfite and the Potassium Persulphate-S-WAT.