Cationic organic silicon modified polyurethane as well as preparation method and application thereof

Abstract

The invention discloses a preparation method of cationic organic silicon modified polyurethane. The preparation method comprises the following steps: carrying out prepolymerization reaction on isocyanate, first polyhydric alcohol, second polyhydric alcohol and third polyhydric alcohol; adding a solvent and a chain extender into the reaction system to carry out chain extension reaction; after the chain extension reaction is completed, adding a cationic hydrophilic agent and a catalyst for reaction; adding acid to neutralize the system; adding deionized water for high-speed dispersion and emulsification, and adjusting the solid content; the textile product using the polyurethane is more washable and has an elastic bony feeling.

Description

Technical Field

[0001] The invention relates to a cationic organosilicon-modified polyurethane and a preparation method and application thereof. Background Art

[0002] In high-end textile finishing applications, especially in nylon and wool fabrics, traditional finishing agents are amino silicone oil and ternary block modified silicone. Although they improve the smoothness and softness of the fabric, they cannot achieve the effect of fabric texture and rebound, and the number of washing times is not enough; while water-based polyurethane resin has the characteristics of rubber elasticity, high adhesion to fabrics, and good water washing resistance. The combination of the two can effectively make up for the shortcomings of silicone performance; however, water-based polyurethane is generally anionic or non-ionic, and there are not many cationic systems. How to develop cationic silicone modified polyurethane based on the characteristics of textile finishing cations to improve the water washing resistance and elastic texture of textile products is the direction that technicians in this field are committed to researching. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing a cationic silicone-modified polyurethane to solve the problems raised in the above background technology.

[0004] To achieve the above object, the present invention provides the following technical solution: a method for preparing a cationic silicone-modified polyurethane, comprising the following steps:

[0005] (1) subjecting isocyanate, a first polyol, a second polyol and a third polyol to a prepolymerization reaction;

[0006] (2) adding a solvent and a chain extender to the system after the reaction in step (1) is completed to carry out a chain extension reaction;

[0007] (3) After the chain extension reaction is completed, a cationic hydrophilic agent and a catalyst are added to react;

[0008] (4) After the reaction in step (3) is completed, adding an acid to neutralize the system;

[0009] (5) adding deionized water to the step (4) for high-speed dispersion and emulsification to adjust the solid content;

[0010] Wherein, the first polyol is one or more of polytetramethylene glycol, polycarbonate polyol, polycaprolactone polyol, and neopentyl glycol adipic acid; the second polyol is one or more of polypropylene oxide polyol, tetramethylene glycol and propylene oxide copolymer polyol, and propylene oxide and ethylene oxide copolymer polyol; the third polyol is one or more of bihydroxyl-terminated silicones having a number average molecular weight of 2000-8000; the cationic hydrophilic agent is one or more of N-methyldiethanolamine and quaternized bihydroxyl-terminated compounds;

[0011] When the polyurethane is modified with cationic silicone, the molar ratio of the isocyanate, the first polyol, the second polyol and the third polyol in step (1) is 3.5-15:0.2-1.8:0.1-1.5:1;

[0012] The molar ratio of the chain extender in step (2) to the isocyanate in step (1) is 0.1-0.5:1; the molar ratio of the cationic hydrophilic agent in step (3) to the isocyanate in step (1) is 0.05-0.3:1.

[0013] As a specific implementation, the reaction temperature of step (1) is controlled at 80-95°C; the reaction temperature of step (2) is controlled at 70-95°C; and the reaction temperature of step (3) is controlled at 95-120°C.

[0014] As a specific embodiment, step (1) is carried out in the absence of a solvent; and steps (2) to (4) are carried out in the presence of a solvent.

[0015] As a specific implementation, the third polyol is one or more bihydroxy-terminated silicones having a number average molecular weight of 3000-5000.

[0016] The isocyanate used in the present invention is one or more of MDI, TDI, HMDI and HDI; the solvent is one or more of methyl pyrrolidone, dimethylformamide, dimethylacetamide and acetone; the chain extender is one or more of trimethylolpropane, ethanolamine, diethylene glycol, ethylene glycol, 1,4-butanediol, neopentyl glycol and isophorone diamine; the acid is one or more of phosphoric acid, oxalic acid, acetic acid, lactic acid and citric acid, etc. The neutralization degree is controlled between 0.85 and 1.1 of the molar number of the cation.

[0017] Step (5) After the acid neutralizes the system, slowly add deionized water, control the speed of the dispersion disk between 500-2000 rpm, stir while adding water, until the emulsion is uniform and free of precipitation, and then filter with a 100-300 mesh filter to obtain the desired product.

[0018] The second object of the present invention is to provide a cationic silicone-modified polyurethane prepared by the above preparation method.

[0019] The third object of the present invention is to provide the application of the cationic silicone modified polyurethane prepared by the above preparation method in textile fabrics.

[0020] As a specific implementation method, the specific process is as follows: the prepared cationic silicone polyurethane emulsion is impregnated and rolled with a rolling concentration of 30g / L, and then placed in a 105°C oven for drying, and then dried and shaped in a high-temperature setting machine at 150°C for 90s.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows: using the cationic silicone polyurethane emulsion prepared by the present invention on textile fabrics can greatly improve the characteristics of textile products in terms of water resistance and elasticity; the preparation method of the present invention does not generate waste gas or waste liquid during operation, and the solvent can be recycled and reused, which has the advantages of being economical and environmentally friendly and is more suitable for industrial production. DETAILED DESCRIPTION

[0022] Unless the context clearly dictates otherwise, unmodified nouns and nouns modified by "the" include singular and plural referents.

[0023] As used in the specification and claims, the terms "comprises," "comprising," "having," "may," "containing," and variations thereof as used herein refer to open transitional phrases, terms, or words that require the presence of specified ingredients / steps and allow for the presence of other ingredients / steps. However, such descriptions should be interpreted as also describing compositions or methods as "consisting of" and "consisting essentially of" the recited ingredients / steps, which allows for the presence of only the specified ingredients / steps and any unavoidable impurities that may result therefrom, and excludes other ingredients / steps.

[0024] Numerical values ​​in the specification and claims of this application should be understood to include the same numerical values ​​when reduced to the same number of significant figures and numerical values ​​that differ from the stated value by less than the experimental error of ordinary measurement techniques of the type described in this application for determining the stated value.

[0025] All ranges disclosed herein are inclusive of the indicated endpoints and are independently combinable (eg, the range of "2 grams to 10 grams" includes the endpoints 2 grams and 10 grams, and all intermediate values).

[0026] The terms "about" and "approximately" can be used to include any numerical value that can be varied without changing the basic function of the value. When used with a range, "about" and "approximately" also disclose the range defined by the absolute values ​​of the two endpoints, for example, "about 2 to about 4" also discloses a range of "2 to 4". Generally, the terms "about" and "approximately" can refer to ±10% of the indicated number. However, for temperature, the term "approximately" refers to ±1°C.

[0027] Unless expressly stated otherwise, the percentages of elements are to be considered as percentages by weight of the alloy in question.

[0028] The present disclosure may refer to the temperature of certain method steps. It should be noted that these specifications generally refer to the temperature set by the heat source (such as a furnace), and not necessarily the temperature that the heated material must reach.

[0029] The present invention provides a method for preparing a cationic silicone-modified polyurethane, comprising the following steps:

[0030] (1) subjecting isocyanate, a first polyol, a second polyol and a third polyol to a prepolymerization reaction;

[0031] (2) adding a solvent and a chain extender to the system after the reaction in step (1) is completed to carry out a chain extension reaction;

[0032] (3) After the chain extension reaction is completed, a cationic hydrophilic agent and a catalyst are added to react;

[0033] (4) After the reaction in step (3) is completed, adding an acid to neutralize the system;

[0034] (5) adding deionized water to the step (4) for high-speed dispersion and emulsification to adjust the solid content;

[0035] Wherein, the first polyol is one or more of polytetramethylene glycol, polycarbonate polyol, polycaprolactone polyol, and neopentyl glycol adipic acid; the second polyol is one or more of polypropylene oxide polyol, tetramethylene glycol and propylene oxide copolymer polyol, and propylene oxide and ethylene oxide copolymer polyol; the third polyol is one or more of bihydroxyl-terminated silicones having a number average molecular weight of 2000-8000; the cationic hydrophilic agent is one or more of N-methyldiethanolamine and quaternized bihydroxyl-terminated compounds;

[0036] When the polyurethane is modified with cationic silicone, the molar ratio of the isocyanate, the first polyol, the second polyol and the third polyol in step (1) is 3.5-15:0.2-1.8:0.1-1.5:1;

[0037] The molar ratio of the chain extender in step (2) to the isocyanate in step (1) is 0.1-0.5:1; the molar ratio of the cationic hydrophilic agent in step (3) to the isocyanate in step (1) is 0.05-0.3:1.

[0038] Here, the reaction temperature of step (1) is controlled to be 80-95°C; the reaction temperature of step (2) is controlled to be 70-95°C; the reaction temperature of step (3) is 95-120°C; step (1) is reacted in the absence of a solvent; steps (2)-(4) are reacted in the presence of a solvent.

[0039] Embodiment 1

[0040] In a clean 500 ml four-necked flask, put polyester polyol XCP2000, polyether polyol 220, and hydroxyl-terminated silicone, dehydrate at 120°C in vacuum for 2 hours, cool to about 90°C, add isophorone diisocyanate, keep it at about 90°C for reaction for 2 hours, add solvent, cool to about 75°C, add chain extender trimethylolpropane, 1,4-butanediol and isophorone diamine, keep the temperature for 2 hours, then add cationic hydrophilic chain extender N-methyldiethanolamine and catalyst, heat to about 110°C, keep it for 3 hours, cool to 60°C, add acid for neutralization, and then transfer to a high-speed dispersion cup, start the dispersion disk, rotate at about 1000 rpm, slowly add deionized water until phase inversion occurs, the emulsion is milky white with blue light, and filter out the material after standing for 12 hours. The specific ratio is shown in Table 1.

[0041] Here, the first polyol uses polyester polyol XCP2000 purchased from Asahikawa Chemical Co., Ltd., model XCP2000, with a number average molecular weight of about 2000; the second polyol uses polyether polyol purchased from Dow Chemical, model polyether 200, with a number average molecular weight of about 2000; the terminal hydroxyl silicone uses terminal hydroxyl silicone model 3402E produced by Aosjia New Materials Technology Research (Jiangsu) Co., Ltd., with a number average molecular weight of about 2000; isophorone diisocyanate uses Evonik Degussa Special Chemicals (Shanghai) Co., Ltd.

[0042] Table 1

[0043]

[0044]

[0045] The changes from Example 1 to Example 5 are: the content of terminal hydroxyl silicone increases from 0 to 50% (solid content percentage), and the effects of different contents of silicone on the softness and water resistance of the fabric are investigated. The appearance of the prepared emulsion changes from clear to milky white, indicating that the emulsion particle size begins to increase with the increase of silicone. This can be well demonstrated by the Malvern particle size analyzer: the particle size distribution gradually changes from about 100 nanometers to around 230 nanometers, so the silicone content is generally controlled below 50%. If it is more, demulsification will occur.

[0046] The cationic silicone-modified polyurethane emulsion obtained in Examples 1-5 above was used to treat textile fabrics, specifically:

[0047] The fabric is wetted and rolled with a rolling liquid concentration of 30g / L, then dried in a 105-degree oven, and then dried and fixed in a high-temperature setting machine at 150 degrees for 90 seconds. The fabric here is nylon.

[0048] The performance of the above-mentioned impregnated fabrics was tested, and the test results are shown in Table 2.

[0049] Table 2

[0050]

[0051]

[0052] Smoothness, bulk and elasticity are evaluated according to industry standards.

[0053] The water washing test is carried out in accordance with GB / T3921.1-1997.

[0054] From the results in Table 2, it can be seen that the silicone content is relatively stable between 25-37.5%, preferably 37.5%; compared with ordinary silicone softeners without polyurethane, the structure of polyurethane does effectively improve the elasticity and water resistance, which indirectly proves that the elasticity of the skin is better, and the formula of Example 4 is preferred; in addition, the polyurethane is more obviously washable in terms of water washing, so the present invention has the elasticity and washability functions of making up for the traditional silicone softener, and the combination of the two is one of the future development directions.

[0055] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a cationic silicone-modified polyurethane, characterized in that: The following steps are involved: (1) subjecting isocyanate, a first polyol, a second polyol and a third polyol to a prepolymerization reaction; (2) adding a solvent and a chain extender to the system after the reaction in step (1) is completed to carry out a chain extension reaction; (3) After the chain extension reaction is completed, a cationic hydrophilic agent and a catalyst are added to react; (4) After the reaction in step (3) is completed, adding an acid to neutralize the system; (5) adding deionized water to the mixture in step (4) for high-speed dispersion and emulsification to adjust the solid content; Wherein, the first polyol is one or more of polytetramethylene glycol, polycarbonate polyol, polycaprolactone polyol, and neopentyl glycol adipic acid; the second polyol is one or more of polypropylene oxide polyol, tetramethylene glycol and propylene oxide copolymer polyol, and propylene oxide and ethylene oxide copolymer polyol; the third polyol is one or more of bihydroxyl-terminated silicones having a number average molecular weight of 2000-8000; the cationic hydrophilic agent is one or more of N-methyldiethanolamine and quaternized bihydroxyl-terminated compounds; When the cationic silicone-modified polyurethane is used, the molar ratio of the isocyanate, the first polyol, the second polyol and the third polyol in step (1) is 3.5-15:0.2-1.8:0.1-1.5:1; The molar ratio of the chain extender in step (2) to the isocyanate in step (1) is 0.1-0.5:1; the molar ratio of the cationic hydrophilic agent in step (3) to the isocyanate in step (1) is 0.05-0.3:

1.

2. The method for preparing a cationic silicone-modified polyurethane according to claim 1, characterized in that: The reaction temperature of step (1) is controlled to be 80-95°C; the reaction temperature of step (2) is controlled to be 70-95°C; and the reaction temperature of step (3) is controlled to be 95-120°C.

3. The method for preparing a cationic silicone-modified polyurethane according to claim 1, characterized in that: The step (1) is carried out in the absence of a solvent; the steps (2) to (4) are carried out in the presence of a solvent.

4. A cationic silicone-modified polyurethane prepared by the preparation method according to any one of claims 1 to 3.

5. Use of the cationic silicone-modified polyurethane prepared by the preparation method according to any one of claims 1 to 3 on textile fabrics.

6. The use of a cationic silicone-modified polyurethane on textile fabrics according to claim 4, characterized in that: The specific process is as follows: the prepared cationic silicone polyurethane emulsion is impregnated and rolled with a rolling concentration of 30g / L, and then placed in a 105°C oven for drying, and then dried and shaped in a high-temperature setting machine at 150°C for 90s.

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