CN107793546B - A kind of cationic-nonionic mixed water-based polyurethane and its preparation method and application - Google Patents

Abstract

The invention discloses a cation-nonionic mixed water-based polyurethane, which is prepared from the following components in parts by weight: 18-30 parts of non-ionic hydrophilic monomer, 30-50% of polyether diol, diisocyanate 20% to 35%, 4 to 7 parts of chain extender, 2 to 6 parts of neutralizing acid. It can be used as one of the components in textile sizing, and can be stably dispersed in neutral or even weakly acidic (pH=5-7) textile sizing when diluted to 20-100 times. The material is not easy to play the role of bristle breakage during the spinning process.

Description

A kind of cationic-nonionic mixed water-based polyurethane and its preparation method and application

technical field

The invention relates to the field of chemical industry, in particular, to a cationic-nonionic mixed water-based polyurethane and a preparation method and application thereof.

Background technique

Textile pulp is a general term for natural and synthetic water-soluble or water-dispersible polymers with viscous properties used in the pretreatment of textile fibers. These polymers can be uniformly mixed in water and remain stably dispersed after cooking. , which is evenly attached to the surface of textile fibers during the spinning process, so that the fibers are continuously filamentous and lint-free during the spinning process, and it is easy to quickly desize in alkaline water after the spinning process is completed. The main components of conventional textile size include starch and its derivatives, polyvinyl alcohol (PVA), acrylic or polyester binders, post-waxing auxiliaries, mildew inhibitors, moisture absorbents, and the like. At present, the mainstream products in the market such as polyvinyl alcohol, water-based acrylic acid and other products are generally in the ratio of 1:4 to 1:2 due to their poor wear resistance and strength, and the quality ratio of starch is generally between 1:4 and 1:2. , and caused the problem of subsequent waste liquid treatment.

As a new low-VOC environmentally friendly product, water-based polyurethane has the advantages of high strength, good elasticity and good wear resistance compared with polyvinyl alcohol and water-based acrylate dispersions. However, the traditional anionic water-based polyurethane has the following defects: a. It is sensitive to pH value, and has poor stability after being diluted 20-100 times in water. Modified starch, polyvinyl alcohol, and some filler auxiliaries used in textile pulp It is usually weakly acidic, and the conventional anionic water-based polyurethane is easily mixed with it to form flocs after demulsification and agglomeration, which seriously affects the dispersion effect and spinning efficiency of pulp cooking; b. Because water-based polyurethane is more hydrophilic than polyvinyl alcohol , The water-based acrylate dispersion is poor, so the post-treatment desizing efficiency is low; c. The price of traditional anionic water-based polyurethane is more expensive than that of polyvinyl alcohol and acrylic resin. The efficiency improvement is not obvious, resulting in a small scale of promotion of waterborne polyurethane in the textile pulp industry.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide a cationic-nonionic mixed water-based polyurethane, which can be used as one of the components in the textile pulp, and can be diluted to 20 to 100 times in the case of It is stably dispersed in neutral or even weakly acidic (pH=5-7) textile sizing, and has the effect of making the sizing of the textile less prone to breakage during spinning.

For solving the above problems, the technical scheme adopted in the present invention is as follows:

The present invention includes a cationic-nonionic mixed water-based polyurethane, which is prepared from the following components in parts by weight:

Preferably, the non-ionic hydrophilic monomer is one of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene monostearate or several.

Preferably, the polyether diol is one or more of polyether N-205, polyether N-210, polyether N-220 and polyether N-330.

Preferably, the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and carbodiimide-modified MDI.

Preferably, the chain extender is methyldiethanolamine.

The neutralizing acid is one or more of acetic acid, 2-hydroxypropionic acid and butyric acid.

The present invention also includes a preparation method of a cationic-nonionic mixed water-based polyurethane, comprising:

1) The non-ionic hydrophilic monomer and polyether diol are heated to 100℃～125℃ and then vacuum dehydrated;

2) cooling the product after the vacuum dehydration treatment in step 1) to 50° C. to 60° C., adding diisocyanate at one time and carrying out heat preservation treatment;

3) Cool the product after the heat preservation treatment in step 2) to 30°C to 40°C, dropwise add the acetone solution containing the chain extender, add neutralizing acid after the dropwise addition and stir, and then add deionized water under high-speed dispersion to carry out emulsification;

4) The product after the emulsification treatment in the step 3) is heated to 60°C to 75°C, and the acetone is removed under vacuum conditions to obtain the obtained product.

Further, the step 3) can be replaced by, cooling to 30 ℃～40 ℃, adding dropwise the acetone solution containing the chain extender, adding neutralizing acid after the dropwise addition, stirring, and then adding deionized water under high-speed dispersion to carry out. Emulsifying treatment; or, cooling to 30°C to 40°C, dropwise adding acetone solution containing chain extender, after dropwise addition, adding neutralizing acid-containing deionized aqueous solution under high-speed dispersion for emulsifying treatment.

Further, in the step 1), the vacuum dehydration treatment is specifically vacuum dehydration for 1.5-2.5 h, and the vacuum degree is between 0.08 and 1.0 MPa; in the step 2), the heat preservation treatment is specifically the heat preservation at 50°C to 70°C 2.5-3.5h; in the step 3), the acetone solution containing the chain extender is an acetone solution containing the chain extender with a mass concentration of 7.5% to 15%, and the dropwise addition time of the acetone solution containing the chain extender is 30min～15%. For 1 h, the stirring rate of the high-speed dispersion is 500-2000 r/min; in the step 4), the vacuum condition is specifically a vacuum degree between 0.04-1.0 MPa.

The present invention also includes the application of cationic-nonionic mixed water-based polyurethane in textile pulp.

The present invention also includes a preparation method of textile pulp, comprising:

a) Add deionized water into the reaction flask, add starch for textile size under stirring, wherein the stirring speed is 120～240r/min, and the stirring time is 5～10min;

b) Add the cationic-nonionic water-based polyurethane into the reaction flask, heat the temperature to 95°C to 100°C, and boil the pulp for 20-40 minutes, that is, it is obtained.

Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention provides a cationic-nonionic mixed water-based polyurethane, which can be used as one of the components to be used in textile pulp, and can be diluted to 20-100 times in a It can be stably dispersed in neutral or even weakly acidic (pH=5-7) textile sizing under certain circumstances, and has the effect of making the sizing of the textile less prone to breakage during spinning. The preparation process of the textile slurry prepared by the cationic-nonionic water-based polyurethane in the present invention is relatively simple and easy to operate. Since the cationic-nonionic water-based polyurethane is a viscous liquid, it is easy to disperse evenly in water, and the whole pulping process only takes 40min-1h, which greatly saves manpower and material resources; The requirements are correspondingly lower; at the same time, the amount of cationic-nonionic water-based polyurethane is lower than that of polyvinyl alcohol, so the generated waste liquid is easier to handle, and it is an environmentally friendly material.

Description of drawings

Fig. 1 is the molecular formula of polyoxyethylene sorbitan monostearate (Tween 60);

Figure 2 is a schematic diagram of the "core-shell structure" of the cationic-nonionic hybrid waterborne polyurethane in the present invention.

Detailed ways

The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

The present invention includes: The present invention relates to a cationic-nonionic mixed water-based polyurethane, which is prepared from the following components in parts by weight: 18-30 parts of non-ionic hydrophilic monomers, 30%-50% of polyether diol, 20% to 35% of diisocyanate, 4 to 7 parts of chain extender, and 2 to 6 parts of neutralizing acid.

Preferably, the non-ionic hydrophilic monomer is polyoxyethylene sorbitan monostearate (Tween 60), polyoxyethylene sorbitan tristearate (Tween 65), polyoxyethylene sorbitan monostearate (Tween 65), and polyoxyethylene sorbitan monostearate (Tween 65). Fatty acid ester. As shown in Figures 1 and 2, Tween 60 is a non-ionic emulsifier, which contains non-ionic polyoxyethylene groups -CH ₂ CH ₂ -O- and stearic acid -C ₁₈ H ₃₈ hydrophobic groups and hydroxyl-OH groups capable of reacting with isocyanates. Tween 65, polyoxyethylene monostearate and Tween 60 have similar structural characteristics, both contain non-ionic hydrophilic polyoxyethylene groups -CH ₂ CH ₂ -O-, and have long-chain alkane hydrophobic groups. When the non-ionic hydrophilic monomer participates in the synthesis of polyurethane, on the one hand, polyoxyethylene-CH ₂ CH ₂ -O- groups are introduced into the molecular segment of the polyurethane, which improves the hydrophilicity of the molecular segment, thereby forming a non-ionic type. One of the "shell structure" components in the "core-shell structure" of water-based polyurethane, while the chain extender methyldiethanolamine is neutralized by acid to form a quaternary ammonium salt cation, which constitutes the "core-shell structure" of the cationic water-based polyurethane. It is one of the "shell structure" components, which together form the hydrophilic phase of the non-ionic-cationic hybrid water-based polyurethane, and dissolves into water; on the other hand, hydrophobic groups such as stearic acid-C ₁₈ H ₃₈ The same hydrophobic groups as in the main chain of polyurethane, such as urethane bonds, together form the "core structure" component in the "core-shell structure", and then the "core-shell structure" can be obtained at pH=5～7. A stable dispersion of cationic-nonionic hybrid waterborne polyurethane in textile pulp.

In the weakly acidic to neutral textile pulp with pH value of 5-7, the system contains more cationic H ⁺ , and the non-ionic-cationic water-based polyurethane contains quaternary ammonium salt type cation, and the quaternary ammonium salt type cation and the pulp system The same charge of H ⁺ repels each other, so as to stably disperse; at the same time, the hydrophilicity of the non-ionic hydrophilic group is completely unaffected by H ⁺ and pH value, so the non-ionic-cationic hybrid water-based polyurethane It can be stably dispersed in neutral or even weakly acidic textile pulp when diluted to 20-100 times.

Preferably, the polyether diol is one or more of polyether N-205, polyether N-210, polyether N-220 and polyether N-330. The diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and carbodiimide-modified MDI. The chain extender is methyldiethanolamine. The neutralizing acid is one or more of acetic acid, 2-hydroxypropionic acid and butyric acid.

The present invention also includes a preparation method of a cationic-nonionic mixed water-based polyurethane, comprising:

1) The non-ionic hydrophilic monomer and polyether diol are heated to 100℃～125℃ and then vacuum dehydrated;

2) cooling the product after the vacuum dehydration treatment in step 1) to 50° C. to 60° C., adding diisocyanate at one time and carrying out heat preservation treatment;

3) Cool the product after the heat preservation treatment in step 2) to 30°C to 40°C, dropwise add the acetone solution containing the chain extender, add neutralizing acid after the dropwise addition and stir, and then add deionized water under high-speed dispersion to carry out emulsification;

4) The product after the emulsification treatment in the step 3) is heated to 60°C to 75°C, and the acetone is removed under vacuum conditions to obtain the obtained product.

Further, the step 3) can be replaced by, cooling to 30 ℃～40 ℃, adding dropwise the acetone solution containing the chain extender, adding neutralizing acid after the dropwise addition, stirring, and then adding deionized water under high-speed dispersion to carry out. Emulsifying treatment; or, cooling to 30°C to 40°C, dropwise adding acetone solution containing chain extender, after dropwise addition, adding neutralizing acid-containing deionized aqueous solution under high-speed dispersion for emulsifying treatment.

Further, in the step 1), the vacuum dehydration treatment is specifically vacuum dehydration for 1.5-2.5 h, and the vacuum degree is between 0.08 and 1.0 MPa; in the step 2), the heat preservation treatment is specifically the heat preservation at 50°C to 70°C 2.5-3.5h; in the step 3), the acetone solution containing the chain extender is an acetone solution containing the chain extender with a mass concentration of 7.5% to 15%, and the dropwise addition time of the acetone solution containing the chain extender is 30min～15%. For 1 h, the stirring rate of the high-speed dispersion is 500-2000 r/min; in the step 4), the vacuum condition is specifically a vacuum degree between 0.04-1.0 MPa.

The invention also includes the application of a cationic-nonionic mixed water-based polyurethane in textile pulp.

The present invention also includes a preparation method of textile pulp, comprising:

a) Add deionized water into the reaction flask, add starch for textile size under stirring, wherein the stirring speed is 120～240r/min, and the stirring time is 5～10min;

b) Add the cationic-nonionic water-based polyurethane into the reaction flask, heat the temperature to 95°C to 100°C, and boil the pulp for 20-40 minutes, that is, it is obtained.

Example 1

1.1. Preparation of cationic-nonionic hybrid waterborne polyurethane WPU-1

100g polyether N-210 and 50g polyoxyethylene sorbitan monostearate (Tween 60) were added to the reaction flask, the temperature was raised to 120°C, dehydrated in vacuum for 2h, and the vacuum degree was 0.09MPa; cooled to 50°C, 88.8g IPDI was added , slowly heat up to 70°C for 3h; cool down to 35°C and slowly add 150g of mixed solution (including 15g of methyldiethanolamine, 135g of acetone) dropwise, add 11.3g of lactic acid to neutralize and stir after 1h of dropwise addition; add 492g under high-speed dispersion Emulsify with deionized water, stir at a rate of 1000 r/min, and disperse at a high speed for 1 h; raise the temperature to 50 °C to remove the acetone under vacuum, and then discharge the material to obtain WPU-1. The solid content of WPU-1 is 35%, the appearance is translucent, the viscosity is 8160mPa·s, and the pH value is 6.0.

1.2. Preparation of textile pulp JL-1 containing WPU-1

Add 88g of deionized water to the reaction flask, add 9g of acidic starch under stirring, stir at a rate of 120r/min, and stir for 5min; add 3g of WPU-1, heat up to 95°C and boil for 30min, then cool down and discharge to obtain JB- 1. The solid content of JB-1 is 10%, the appearance is milky white and turbid, the pH value is 6.2, and the viscosity is 22S.

Example 2

2.1. Preparation of cationic-nonionic hybrid waterborne polyurethane WPU-2

Add 100g polyether N-220 and 60g polyoxyethylene sorbitan tristearate to the reaction flask

(Tween 65) heated to 115°C, dehydrated in vacuum for 2h, vacuum degree 0.15MPa; cooled to 55°C, added 55.9g TDI-80, slowly heated to 65°C and kept for 3h; cooled to 30°C and slowly added dropwise 150g of mixed solution (among which methyl Diethanolamine 17.9g, acetone 132.1g), add 12.15g of lactic acid to neutralize and stir after 1h of dropwise addition; add 568g of deionized water for emulsification under high-speed dispersion, stir at 1000r/min, and disperse at high speed for 1h; heat up to 50°C under vacuum After the acetone is removed, the material is discharged to obtain WPU-2. The solid content of WPU-2 is 35%, the appearance is slightly yellow and translucent, the viscosity is 4712mPa"s, and the pH value is 6.5.

2.2. Preparation of textile pulp JL-2 containing WPU-2

Add 88g of deionized water to the reaction flask, add 9g of acidic starch under stirring, stir at a rate of 120r/min, and stir for 5min; add 3g of WPU-2, heat up to 95°C and boil for 30min, then cool down and discharge to obtain JB- 2. The solid content of JB-2 is 10%, the appearance is milky white and turbid, the pH value is 6.3, and the viscosity is 22S.

Example 3

3.1. Preparation of cationic-nonionic hybrid waterborne polyurethane WPU-3

100g of polyether N-205 and 50g of polyoxyethylene monostearate were added to the reaction flask, and the temperature was raised to 125°C, dehydrated in vacuum for 2 hours, and the vacuum degree was 0.3MPa; Incubate at ℃ for 3h; cool down to 30℃ and slowly add 150g of mixed solution (including 15g of methyldiethanolamine and 135g of acetone) dropwise, add 10.2g of lactic acid to neutralize and stir after 1h of dropwise addition; add 470.8g of deionized water to emulsify under high-speed dispersion , the stirring speed is 1000r/min, and the high-speed dispersion is performed for 1h; the temperature is raised to 50°C and the acetone is vacuumed to remove the acetone, and then the material is discharged to obtain WPU-3. The solid content of WPU-3 is 35%, the appearance is slightly yellow and translucent, the viscosity is 5280mPa"s, and the pH value is 6.5.

3.2. Preparation of textile pulp JL-3 containing WPU-3

Add 88g of deionized water to the reaction flask, add 9g of acid starch under stirring, stir at a rate of 120r/min, and stir for 5min; add 3g of WPU-3, heat up to 95°C and boil for 30min, then cool down and discharge to obtain JB- 3. The solid content of JB-3 is 10%, the appearance is milky white and turbid, the pH value is 6.3, and the viscosity is 22S.

Example 4

4.1. Preparation of cationic-nonionic hybrid waterborne polyurethane WPU-4

90g of polyether N-210 and 50g of polyoxyethylene sorbitan monostearate (Tween 60) were added to the reaction flask, and the temperature was raised to 120°C, dehydrated in vacuum for 2 hours, and the degree of vacuum was 0.09MPa; cooled to 50°C, 80.8g of IPDI was added. , slowly heat up to 70°C for 3h; cool down to 35°C and slowly add 150g of mixed solution (including 15g of methyldiethanolamine and 135g of acetone) dropwise, add 12g of lactic acid after 1h of dropwise addition to neutralize and stir; under high-speed dispersion, add 492g to remove Ionized water was emulsified, the stirring rate was 1500 r/min, and the high-speed dispersion was performed for 1 h; the temperature was raised to 50 °C and the acetone was removed by vacuum, and the material was discharged to obtain WPU-4. The solid content of WPU-4 is 35%, the appearance is translucent, the viscosity is 7560mPa·s, and the pH value is 6.0.

4.2. Preparation of textile pulp JL-4 containing WPU-4

Add 102.3g of deionized water to the reaction flask, add 10g of acid starch under stirring, stir at a rate of 120r/min, and stir for 5min; add 4g of WPU-4, heat up to 95°C and boil for 30min, cool down and discharge to obtain JB -4. The solid content of JB-4 is 10%, the appearance is milky white and turbid, the pH value is 6.2, and the viscosity is 23S.

Example 5

5.1. Preparation of cationic-nonionic hybrid waterborne polyurethane WPU-2

85g polyether N-220 and 60g polyoxyethylene sorbitan tristearate (Tween 65) were added to the reaction flask, the temperature was raised to 125°C, dehydrated in vacuum for 2h, and the vacuum degree was 0.15MPa; the temperature was lowered to 55°C and 65.8g TDI was added. -80, slowly heat up to 65°C for 3h; cool down to 30°C and slowly dropwise add 150g of the mixed solution (including 15.7g of methyldiethanolamine, 134.3g of acetone), add 12.15g of lactic acid after the dropwise addition for 1h to neutralize and stir; Under dispersion, 568 g of deionized water was added for emulsification, the stirring rate was 1000 r/min, and the high-speed dispersion was performed for 1 h; the temperature was raised to 50 °C and the acetone was vacuumed to remove the material to obtain WPU-4. The solid content of WPU-4 is 35%, the appearance is slightly yellow and translucent, the viscosity is 5312mPa"s, and the pH value is 6.5.

5.2. Preparation of textile pulp JL-5 containing WPU-4

Add 102.3g of deionized water to the reaction flask, add 10g of acid starch under stirring, stir at a rate of 120r/min, and stir for 5min; add 5g of WPU-5, heat up to 95°C, boil for 30min, cool down and discharge to obtain JB -5. The solid content of JB-5 is 10%, the appearance is milky white and turbid, the pH value is 6.3, and the viscosity is 23S.

Example 6

Preparation of Textile Size JL-0 Containing Polyvinyl Alcohol PVA17-99

Add 153g of deionized water to the reaction flask, add 10g of acid starch under stirring, stir at a rate of 240r/min, and stir for 30min; add 7g of PVA17-99, heat up to 100°C and cook for 3h, then cool down and discharge to obtain JB-0 . The solid content of JB-0 is 10%, the appearance is milky white and turbid, the pH value is 6.0, and the viscosity is 31S.

In the above-mentioned embodiment, the viscosity of WPU-1～WPU-5 is rotational viscosity, according to the national standard GB/T2794-2013 at 25 ℃; The pH value of WPU-1~WPU-5 and JL-1~JL-5 was measured by using a pH meter at 25 ℃ according to the national standard GB/T_6920-1986; the viscosity of JL-0~JL-5 was the coating 4-cup viscosity, measured at 25°C according to the national standard GB/T1723-1993.

Performance comparison:

The textile slurry samples in the above examples and comparative examples were sent to the Mortar Textile Center of Donghua University Textile College for testing. The performance results after testing are shown in Table 1 below.

Table 1 Comparison of properties of textile sizing prepared by cationic-nonionic water-based polyurethane and polyvinyl alcohol

JL-1 JL-2 JL-3 JL-4 JL-5 JL-0 Sizing rate/% 10.7 10.2 10.4 10.9 10.8 10.8 Wear/time 44.9 42.7 43.6 51.6 50.9 43.5 Reduction rate/% 9.7 9.2 9.3 10.5 10.2 10.7 Elongation/% 6.1 5.9 5.4 7.6 7.8 5.8 Strong/CN 271.4 272.4 270.3 281.0 278.2 275.7 Number of regenerated hairiness (1mm/10m) 48.3 48.1 48.7 47.1 46.2 50.0

It can be seen from Table 1 that the detection performances of textile sizing agents JL-1 to JL-5 prepared with cationic-nonionic aqueous polyurethane are all close to or better than JL-0. Among them, the number of regenerated hairiness, which is a particularly important performance parameter in the textile size, is lower than that of the textile size prepared by cationic-nonionic water-based polyurethane, which indicates that the former has a relatively low degree of fluff during spinning, and the spinning size is lower than that of JL-0. The yarn efficiency is relatively high, and the amount of cationic-nonionic waterborne polyurethane in JL-1 to JL-5 is lower than that of polyvinyl alcohol in JL-0. Therefore, the cationic-nonionic mixed waterborne polyurethane in the present invention can completely replace the polyvinyl alcohol. Vinyl alcohol is used in textile sizing.

For those skilled in the art, various other corresponding changes and deformations can be made according to the technical solutions and concepts described above, and all these changes and deformations should fall within the protection scope of the claims of the present invention.

Claims (8)

1. The cation-nonionic mixed waterborne polyurethane is characterized by being prepared from the following components in parts by weight:

18-30 parts of non-ionic hydrophilic monomer,

30-50 parts of polyether glycol,

18-45 parts of diisocyanate,

4-8 parts of a chain extender,

2-6 parts of a neutralizing acid,

the non-ionic hydrophilic monomer is one or more of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate and polyoxyethylene monostearate,

the cation-nonionic mixed waterborne polyurethane is prepared by a preparation method comprising the following steps:

1) heating the nonionic hydrophilic monomer and the polyether glycol to 100-125 ℃, and then carrying out vacuum dehydration treatment;

2) cooling the product subjected to vacuum dehydration treatment in the step 1) to 50-60 ℃, and carrying out heat preservation treatment after adding diisocyanate at one time;

3) cooling the product subjected to heat preservation treatment in the step 2) to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, adding a neutralizing acid after dropwise adding, stirring, and then adding deionized water under high-speed dispersion for emulsification treatment;

4) heating the product emulsified in the step 3) to 60-75 ℃, and pumping out acetone under a vacuum condition to obtain the emulsified product;

the chain extender is methyl diethanol amine, and the neutralized acid is one or more of acetic acid, 2-hydroxypropionic acid and butyric acid.

2. The cationic-nonionic hybrid aqueous polyurethane as claimed in claim 1, wherein the polyether glycol is one or more of polyether N-205, polyether N-210, and polyether N-220.

3. The cationic-nonionic hybrid aqueous polyurethane according to claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and carbodiimide-modified MDI.

4. A method for preparing the cationic-nonionic mixed aqueous polyurethane as described in any one of claims 1 to 3, comprising:

1) heating the nonionic hydrophilic monomer and the polyether glycol to 100-125 ℃, and then carrying out vacuum dehydration treatment;

2) cooling the product subjected to vacuum dehydration treatment in the step 1) to 50-60 ℃, and carrying out heat preservation treatment after adding diisocyanate at one time;

3) cooling the product subjected to heat preservation treatment in the step 2) to 30-40 ℃, dropwise adding an acetone solution containing a chain extender, adding a neutralizing acid after dropwise adding, stirring, and then adding deionized water under high-speed dispersion for emulsification treatment;

4) heating the product emulsified in the step 3) to 60-75 ℃, and pumping out acetone under a vacuum condition to obtain the product,

the non-ionic hydrophilic monomer is one or more of polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate and polyoxyethylene monostearate.

5. The preparation method of the cationic-nonionic mixed waterborne polyurethane as claimed in claim 4, wherein the temperature in step 3) is reduced to 30 ℃ to 40 ℃, an acetone solution containing a chain extender is added dropwise, and after the dropwise addition, the acetone solution containing a chain extender is added into a deionized water solution containing a neutralizing acid under high-speed dispersion for emulsification treatment.

6. The method for preparing the cationic-nonionic mixed waterborne polyurethane as claimed in claim 4 or 5, wherein in the step 1), the vacuum dehydration treatment is specifically vacuum dehydration for 1.5-2.5h, and the vacuum degree is between 0.08-1.0 MPa; in the step 2), the heat preservation treatment is specifically heat preservation for 2.5-3.5h at 50-70 ℃; in the step 3), the acetone solution containing the chain extender is an acetone solution containing the chain extender with the mass concentration of 7.5-15%, the dripping time of the acetone solution containing the chain extender is 30 min-1 h, and the stirring speed of high-speed dispersion is 500-2000 r/min; in the step 4), the vacuum condition is specifically that the vacuum degree is between 0.04 and 1.0 MPa.

7. Use of the cationic-nonionic mixed aqueous polyurethane according to any one of claims 1 to 3 in textile sizing.

8. The use of the cationic-nonionic hybrid aqueous polyurethane of claim 7 in a textile size, wherein the textile size is prepared by a method comprising:

a) adding deionized water into a reaction bottle, and adding starch for textile sizing agent under a stirring state, wherein the stirring speed is 120-240 r/min, and the stirring time is 5-10 min;

b) adding the cation-nonionic waterborne polyurethane into a reaction bottle, heating to 95-100 ℃, and boiling for 20-40min to obtain the cationic-nonionic waterborne polyurethane.

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