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Environmental-friendly high-solid-content aqueous-polyurethane adhesive for shoes and preparation method thereof

A water-based polyurethane, high-solids technology, applied in the direction of polyurea/polyurethane adhesives, adhesives, adhesive types, etc., can solve the problems of difficult to control the reaction speed, difficult to increase the solid content, and the stickiness needs to be improved. The reaction speed is easier to control, the drying time is short, and the preparation process is pollution-free.

Inactive Publication Date: 2014-07-30
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The water-based polyurethane emulsion synthesized by carboxylate-type hydrophilic monomer alone has a high viscosity, and it is difficult to increase the solid content (about 35%); the water-based polyurethane emulsion prepared by using sulfonate-type hydrophilic monomer has high solid content and crystallinity High characteristics, US patent US-5432228 (Bayer company) uses sodium ethylenediamine ethanesulfonate as a hydrophilic chain extender, and successfully synthesized a water-based polyurethane adhesive with a solid content of 50%, but the crystallization is too fast, Viscosity needs to be improved
The cross-linking monomer in domestic polyurethane synthesis mainly adopts trimethylolpropane, such as CN-102516920, CN-102827571, the three hydroxyl groups in the trimethylolpropane molecule have the same reactivity as the isocyanate group, the reaction speed is difficult to control, and it is easy to coagulate. Glue, not conducive to production

Method used

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  • Environmental-friendly high-solid-content aqueous-polyurethane adhesive for shoes and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Dissolve dimethylolpropionic acid and ethylene glycol with a molar ratio of 1 in acetone 9.5 times the mass of ethylene glycol, heat up to 55°C, add 0.02% ethylene glycol mass fraction of 98.3% catalyst Concentrated sulfuric acid was reacted under constant temperature reflux for 24 hours, and the solvent and product water were distilled off under reduced pressure to obtain a new type of cross-linking monomer.

[0022] Table 1 is the raw material formula composition and consumption of present embodiment 1. Add the formula amount of poly-1,4-butylene adipate (molecular weight: 2000) into a polymerization reactor equipped with a digital display electric mixer and a thermometer, raise the temperature to 110°C, distill under reduced pressure to remove water, and keep warm to remove water The time is 2 hours, and the temperature is lowered to 65° C. after the water removal is completed. Add the catalysts dibutyltin dilaurate and isophorone diisocyanate into the reactor, rais...

Embodiment 2

[0026] Dissolve dimethylol butyric acid and ethylene glycol with a molar ratio of 1.05 in acetone with 11 times the mass of ethylene glycol, raise the temperature to 65°C, and add 0.4% ethylene glycol with a mass fraction of 98.3% of the catalyst Concentrated sulfuric acid was reacted under constant temperature reflux for 32 hours, and the solvent and product water were distilled off under reduced pressure to obtain a new type of cross-linking monomer.

[0027] Table 2 is the raw material formula composition and consumption of present embodiment 2. Add the formula amount of poly-1,4-butylene adipate into the polymerization reactor equipped with a digital display electric mixer and a thermometer, raise the temperature to 115°C, distill and remove water under reduced pressure, and keep warm for 2 hours to remove water. After the water removal is completed, the temperature is lowered to 60°C. Add the catalysts dibutyltin dilaurate and isophorone diisocyanate into the reactor, ra...

Embodiment 3

[0031] Dissolve dimethylolpropionic acid and propylene glycol with a molar ratio of 1 in acetone 10 times the mass of propylene glycol, raise the temperature to 60°C, add 0.2% propylene glycol mass fraction of concentrated sulfuric acid with a catalyst mass fraction of 98.3%, and react under constant temperature reflux After 36 hours, the solvent and product water were distilled off under reduced pressure to obtain a new type of cross-linking monomer.

[0032]Table 3 is the raw material formula composition and consumption of present embodiment 3. Add the formula amount of poly-1,4-butylene adipate into a polymerization reactor equipped with a digital display electric mixer and a thermometer, raise the temperature to 110°C, distill and remove water under reduced pressure, and keep warm for 2 hours to remove water. After the water removal is completed, the temperature is lowered to 70°C. Add the catalysts dibutyltin dilaurate and isophorone diisocyanate into the reactor, raise ...

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Abstract

The invention discloses an environmental-friendly high-solid-content aqueous-polyurethane adhesive for shoes and a preparation method thereof. The preparation method comprises the following steps of: firstly synthesizing novel cross-linking monomers; then carrying out reduced pressure distilling and dewatering on 76-82 parts by mass of polyester polyol, then adding 16-20 parts by mass of polyisocyanate and 0.02-0.03 part by mass of catalysts, and stirring for reaction; adding 0.2-0.4 part by mass of the novel cross-linking monomers and 0.2-0.7 part by mass of chain extenders to continuously react; reducing temperature, adding a solvent and 2-3.1 parts by mass of sulphonate type hydrophilic monomers; carrying out high-speed shearing emulsification on a prepolymer by adding water, and then carrying out chain extension; increasing the temperature, carrying out reduced pressure distilling and removing the solvent; and adding a defoaming agent and a thickening agent to obtain the finished product. The group reaction activity of the novel cross-linking monomers is favorable to controlling reaction speed and preventing burst polymerization. Tests prove that the aqueous-polyurethane adhesive disclosed by the invention basically has no organic solvent residue, has the advantages of excellent mechanical property and good heat-resistant property, is suitable for adhering shoe materials and can substitute the solvent type adhesives for shoes maturely applied in the current market.

Description

technical field [0001] The invention relates to a water-based polyurethane adhesive, in particular to an environment-friendly water-based polyurethane adhesive with high solid content for shoes and a preparation method thereof. The water-based polyurethane adhesive is used for forming and bonding shoe materials. Background technique [0002] my country is the largest shoe-making country in the world. According to statistics, the current annual output of adhesive shoes is more than 2 billion pairs. Polyurethane adhesives have the characteristics of low temperature resistance, good flexibility, strong bonding performance, and good flexibility and hardness adjustability, and their usage in the shoemaking industry is increasing year by year. Polyurethane adhesives in the domestic market are mainly solvent-based, which are prepared by solution polymerization through solvents such as toluene and xylene. A large amount of solvents in the product will cause harm to the human body an...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C09J175/06C08G18/75C08G18/66C08G18/42C08G18/32
Inventor 涂伟萍陈军王锋胡剑青
Owner SOUTH CHINA UNIV OF TECH