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Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof

A technology of cationic polyurethane and acrylic resin, which is applied in the field of resin, can solve the problems of slow drying speed, poor solvent resistance, poor water resistance, etc., achieve the effects of chemical stability of water resistance, outstanding aging resistance, and avoid poor water resistance

Active Publication Date: 2016-03-23
武汉仕全兴聚氨酯科技有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] Water-based polyurethane can be divided into ionic and non-ionic according to whether the dispersed particles are charged, and ionic water-based polyurethane can be divided into anionic, cationic and zwitterionic according to the charging properties of the polyurethane main chain. There are many applications of polyurethane, because the process of quaternizing the prepolymer in the preparation process of quaternary ammonium cationic water-based polyurethane is more complicated, the cost is higher, and the prepared cationic products are sometimes unstable in storage; compared with anionic At present, there are few research reports on cationic type water-based polyurethane. At the same time, water-based cationic polyurethane has disadvantages such as poor water resistance, low gloss, poor solvent resistance, and slow drying speed; but because the molecular chain of cationic water-based polyurethane has positive charges, its It has good wettability to hydrophobic polyester and fabric fibers, and is not sensitive to water hardness, and can be used under acidic conditions, so it has broad application prospects in the fields of textiles, leather, wood coatings, and papermaking; water-based Hydroxy acrylic resin has the advantages of high mechanical strength, aging resistance, good weather resistance and good water resistance, but it also has the disadvantage of hot stickiness and cold brittleness; modifying water-based cationic polyurethane with hydroxy acrylate can maximize the strengths and avoid weaknesses. A water-based cationic polyurethane-hydroxyacrylic resin with improved performance is obtained; and the resin is conveniently compounded with amino resin to prepare water-based cationic amino baking varnish; it can also be compounded with water-based polyisocyanate curing agent to prepare normal temperature self-drying water-based cationic polyurethane double-pack The compounded resin can significantly improve its hardness, water resistance, impact resistance and other properties, which greatly expands the application field of cationic resin
[0003] At the same time, traditional solvent-based cationic polyurethane-acrylic resins use acetone or methyl ethyl ketone method. The use of organic solvents needs to be removed by distillation, which is cumbersome. pollution

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] (1) Under the protection of nitrogen, put 120 parts of maleic anhydride, 130 parts of trimethylolpropane, 480 parts of adipic acid, 550 parts of hexanediol, and 6 parts of p-hydroxymethyl anisole into the belt with stirring, In the four-port reactor with thermometer, nitrogen gas guide tube, condenser, and water separator, the temperature was slowly raised to 140°C, stirring was started, and the temperature was slowly raised to 210°C (the heating time was 5h). After holding at 210°C for 0.5h, start to measure the acid value. When the acid value drops to 5mgKOH / g resin, remove the xylene in a vacuum with a vacuum degree of 0.045Kpa, and dry it under reduced pressure for 1h to obtain the unsaturated hydroxyl-terminated polyester.

[0019] (2) Put 500 parts of the above-mentioned unsaturated hydroxyl-terminated polyester and 230 parts of 1,4-butanediol into a four-port reactor equipped with a stirrer, a thermometer, a nitrogen gas guide tube, and a condenser tube, and at 11...

Embodiment 2

[0022](1) Under nitrogen protection, 120 parts of maleic anhydride, 300 parts of trimethylolpropane monoallyl ether, 480 parts of adipic acid, 650 parts of 2-ethyl-2-butyl 1,3-propanediol , put 8 parts of p-hydroxymethyl anisole into a four-port reactor with stirring, thermometer, nitrogen gas guide tube, condenser, and water separator, slowly heat up to 140°C, start stirring, and slowly heat up to 210°C ( The heating time is 5h); after holding at 210°C for 0.5h, start to measure the acid value, when the acid value drops to 5mgKOH / g resin, vacuum out the xylene, after the reaction is completed, the vacuum degree is 0.045Kpa, and the vacuum pressure is reduced for 1.5h , That is, unsaturated hydroxyl-terminated polyester.

[0023] (2) Add 400 parts of the above-mentioned unsaturated hydroxyl-terminated polyester and 280 parts of 1,4-butanediol into a four-port reactor equipped with a stirrer, a thermometer, a nitrogen gas guide tube, and a condenser tube. , first vacuum pumpin...

Embodiment 3

[0026] (1) Under nitrogen protection, 90 parts of maleic anhydride, 270 parts of trimethylolpropane monoallyl ether, 500 parts of adipic acid, 670 parts of 2-ethyl-2-butyl 1,3-propanediol , put 8 parts of p-hydroxymethyl anisole into a four-port reactor with stirring, thermometer, nitrogen gas guide tube, condenser, and water separator, slowly heat up to 140°C, start stirring, and slowly heat up to 210°C ( The heating time is 5h). After keeping warm at 210°C for 0.5h, start to measure the acid value. When the acid value drops to 5mgKOH / g resin, vacuum out the xylene. After the reaction is completed, the vacuum degree is 0.045Kpa, and the vacuum is dried for 2 hours to obtain unsaturated hydroxyl terminated polyester.

[0027] (2) Add 560 parts of the above-mentioned unsaturated hydroxyl-terminated polyester and 230 parts of 1,4-butanediol into a four-port reactor equipped with a stirrer, a thermometer, a nitrogen gas guide tube, and a condenser tube. , first vacuum pumping w...

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Abstract

The invention provides a preparation method of hydroxyl type water-borne cationic polyurethane-acrylic acid resin. The method comprises the following steps that 1, hydroxyl telechelic polyester containing an unsaturated double bond is obtained through a reaction; 2, a product obtained in the first step serves as the raw material, dihydric alcohol, isocyanate, a hydrophilic monomer, a catalyst, an end-capped reagent, neutralizer and the like are added according to the ratio of a designed formula, and the unsaturated water-borne cationic polyurethane is obtained; 3, a product obtained in the second step serves as the raw material to be reacted with an acrylate monomer according to the ratio of a designed formula, and the hydroxyl type water-borne cationic polyurethane-acrylic acid resin is obtained. The end-capped reagent is added in the second step, double bond monomer end-capping is conducted on a water-borne cationic polyurethane resin prepolymer, and the grafting rate of acrylic acid resin is further increased; the reaction condition is mild, water-borne cationic polyurethane-hydroxyl type acrylic acid resin with improved performance is obtained without adding emulsifier, and the application field of the resin is greatly enlarged.

Description

Technical field: [0001] The invention relates to the field of resins, in particular to a preparation method of hydroxyl-type water-based cationic polyurethane-acrylic resin. Background technique: [0002] Water-based polyurethane can be divided into ionic and non-ionic according to whether the dispersed particles are charged, and ionic water-based polyurethane can be divided into anionic, cationic and zwitterionic according to the charging properties of the polyurethane main chain. There are many applications of polyurethane, because the process of quaternizing the prepolymer in the preparation process of quaternary ammonium cationic water-based polyurethane is more complicated, the cost is higher, and the prepared cationic products are sometimes unstable in storage; compared with anionic At present, there are few research reports on cationic type water-based polyurethane. At the same time, water-based cationic polyurethane has disadvantages such as poor water resistance, lo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F283/00C08F220/18C08F220/14C08F220/28C08F212/08C08F230/08C08G18/67C08G18/66C08G18/42C08G63/52
Inventor 陈俊华成明肖玉新周俊锋
Owner 武汉仕全兴聚氨酯科技有限公司
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