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CN-122011997-A - Preparation method of low-temperature-resistant waterproof moisture-permeable polyurethane adhesive, product and application thereof

CN122011997ACN 122011997 ACN122011997 ACN 122011997ACN-122011997-A

Abstract

The invention relates to a preparation method of a low-temperature-resistant waterproof moisture-permeable polyurethane adhesive, a product and application thereof, wherein diisocyanate and polycarbonate polyol are mixed and reacted in a solvent, and amino silicone oil is added for reaction to obtain a first amino-terminated prepolymer solution; the method comprises the steps of reacting diisocyanate with polyether polyol to obtain an isocyanate-terminated prepolymer solution, reacting the first amino-terminated prepolymer solution with the isocyanate-terminated prepolymer solution to obtain a second amino-terminated prepolymer solution, mixing the second amino-terminated prepolymer solution with a polyisocyanate curing agent, and coating the mixture on a fabric for curing. According to the invention, through molecular structure design, the polyurethane adhesive with low temperature resistance, hydrolysis resistance, moisture permeability and high adhesion is realized, the glass transition temperature of the prepared polyurethane adhesive film is between minus 30 ℃ and minus 10 ℃, the water vapor permeability of the formed adhesive film is 210-300 g/(m 2 h) at the temperature of 38 ℃ and the relative humidity of 50%.

Inventors

  • XIE MING
  • LI JIANSHAN
  • ZHAO YOUZHONG
  • WEI YANLING
  • LIANG YUNSHENG
  • ZHU SHOUJIN

Assignees

  • 康达新材料(集团)股份有限公司

Dates

Publication Date
20260512
Application Date
20260303

Claims (10)

  1. 1. The preparation method of the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive is characterized by comprising the following steps of: Step one, mixing diisocyanate and polycarbonate polyol in a solvent for reaction, and adding amino silicone oil for reaction to obtain a first amino-terminated prepolymer for standby, wherein the first amino-terminated prepolymer is shown in the following structural formula 1: Structural formula 1, wherein R' is a molecular chain connecting two-NCO groups, R1 is a chain segment of poly 1, 6-hexanediol diphenyl carbonate, and R2 is a chain segment of polydimethylsiloxane; step two, mixing diisocyanate and polyether polyol in a solvent for reaction to obtain an isocyanate-terminated prepolymer for standby, wherein the isocyanate-terminated prepolymer is shown in the following structural formula 2: Structural formula 2; Step three, mixing and reacting the first amino-terminated prepolymer and the isocyanate-terminated prepolymer in a solvent to obtain a second amino-terminated prepolymer solution; and step four, mixing the second amino-terminated prepolymer solution with a polyisocyanate curing agent to obtain the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive.
  2. 2. The method for preparing the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive according to claim 1, wherein the diisocyanate is 4, 4-diphenylmethane diisocyanate; The solvent is dimethylacetamide; The polycarbonate polyol is poly-1, 6-hexanediol diphenyl carbonate, the relative molecular weight is 1000-2000, and the molar ratio of the polycarbonate polyol to 4, 4-diphenylmethane diisocyanate is 1:1.5-1:2; The first amino-terminated prepolymer is in the form of a solution having a concentration of 50-60 wt%.
  3. 3. The method for preparing the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive according to claim 2, wherein the amino silicone oil is aminopropyl polydimethylsiloxane, the relative molecular weight is 1000-1800, and the molar ratio of the amino silicone oil to the 4, 4-diphenylmethane diisocyanate is 1:1.5-1:1.
  4. 4. The method for preparing the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive according to claim 1, wherein the reaction temperature of the first step is 80-90 ℃ and the total reaction time is 120-240 min.
  5. 5. The method for preparing the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive according to claim 1, wherein the polyether polyol in the second step is polyethylene glycol with a relative molecular weight of 400-1000; The diisocyanate in the second step is 4, 4-diphenylmethane diisocyanate (MDI); the molar ratio of the polyethylene glycol to the 4, 4-diphenylmethane diisocyanate (MDI) is 1:1.1-1:1.3; The solvent is dimethylacetamide (DMAc); The isocyanate-terminated prepolymer is in a solution form, the concentration of the solution is 50-60 wt%, the reaction temperature of the second step is 80-90 ℃, and the total reaction time is 120-240 min.
  6. 6. The method for preparing a low temperature resistant waterproof moisture permeable polyurethane adhesive according to claim 1, wherein the sequence of the first step and the second step is replaceable.
  7. 7. The method for preparing a low temperature resistant waterproof moisture permeable polyurethane adhesive according to claim 1, wherein the molar ratio of the amino-terminated prepolymer to the isocyanate-terminated prepolymer in the third step is 1.2:1-1.5:1; The solvent is dimethylacetamide (DMAc); the concentration of the amino-terminated prepolymer solution is 50-60 wt%; the reaction temperature of the third step is 80-90 ℃ and the total reaction time is 120-240 min.
  8. 8. The method for preparing the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive according to claim 1, which is characterized in that, The polyisocyanate curing agent in the fourth step is polyisocyanate curing agent TDI-TMP; the mixing mole ratio of the second amino-terminated prepolymer solution to the polyisocyanate curing agent is 0.5:1-1:1; the curing temperature is 40-60 ℃ and the curing time is 24-36 h.
  9. 9. The low-temperature-resistant waterproof and moisture-permeable polyurethane adhesive is obtained by the preparation method of any one of claims 1-8, and is characterized in that the mass fraction of a hard segment structure is 20-35 wt.%, the mass fraction of organosiloxane is 5-10 wt.%, and the mass fraction of a soft segment structure is 55-75 wt.% in one molecular main chain of the low-temperature-resistant waterproof and moisture-permeable polyurethane adhesive.
  10. 10. The application of the low-temperature-resistant waterproof and moisture-permeable polyurethane adhesive according to claim 9, wherein the application is the bonding of textiles in the field of low-temperature resistance, water and moisture permeability, the low-temperature-resistant waterproof and moisture-permeable polyurethane adhesive is cured on the bonding surface of the textiles to form a polyurethane adhesive film structural surface, and the water vapor transmittance of the formed adhesive film is 210-300 g/(m 2 h) under the conditions that the glass transition temperature of the polyurethane adhesive film structural surface is minus 30 to minus 10 ℃ and the relative humidity is 50%.

Description

Preparation method of low-temperature-resistant waterproof moisture-permeable polyurethane adhesive, product and application thereof Technical Field The invention relates to the technical field of polyurethane adhesives, in particular to a preparation method of a low-temperature-resistant waterproof moisture-permeable polyurethane adhesive, a product thereof and application thereof. Background Patent CN 104945594A discloses a hydrolysis-resistant low-temperature-resistant polyurethane adhesive, which adopts polyether segments to replace partial polyester segments, improves the flexibility of the segments, reduces the polarity of molecular chains, and further improves the hydrolysis resistance and low-temperature resistance of the polyurethane adhesive, but has low binding power, and patent CN 121406285A discloses a furyl polyurethane adhesive and a synthesis method thereof, wherein furan amide groups interacted by rigid structures and hydrogen bonds are introduced into a hard segment of polyurethane to construct a microphase separation structure, polyether polyol is used as a soft segment, the glass transition temperature of the segments is reduced, and the adhesive has good low-temperature resistance but poor binding property and moisture permeability. Therefore, development of a polyurethane adhesive which realizes the collaboration of low temperature resistance, hydrolysis resistance, moisture permeability and high adhesion through molecular structure design becomes an urgent need in the field of low temperature resistance, water resistance and moisture permeability adhesion, such as skiing wear fabric adhesion. The skiing wear is used as high-performance outdoor sports equipment and has extremely severe requirements on the composite adhesive of the fabric. The outer layer of the skiing wear is usually a functional nylon fabric, and needs to be firmly compounded with a waterproof moisture permeable film. In cold environments, the adhesive needs to have excellent adhesive strength, low temperature resistance, prevent penetration of snow water, and discharge sweat generated by human body movement to maintain wearing comfort. The existing polyurethane adhesive is difficult to achieve low temperature resistance, waterproof and moisture permeability, the glass transition temperature of the polyester chain segment is high, hardening and brittle fracture are easy to occur in a low-temperature environment, the ester group is not resistant to hydrolysis, the polyether chain segment is excellent in flexibility, good in low temperature resistance and poor in bonding performance due to low polarity, and the organosilane modified polyurethane is good in low temperature resistance, high in microphase separation degree and poor in polarity and moisture permeability when the content is high. In addition, the adhesion force of the existing adhesive to nylon fabric is easily affected by low-temperature environment, and inadequate adhesion force or over-hard adhesive layer can be caused due to improper regulation and control of crosslinking degree, so that the flexibility of the fabric is affected. Disclosure of Invention The invention aims to overcome the defects of the existing polyurethane adhesive that the existing polyurethane adhesive is not resistant to low temperature, poor in hydrolysis resistance and moisture permeability and low in Wen Nianfu force, and provides a preparation method of the low-temperature-resistant waterproof moisture-permeable polyurethane adhesive, a product and application thereof. In order to achieve the purpose, the polyurethane structure with a hydrophobic hard segment compact region and a soft segment hydrophilic region is constructed by utilizing a microphase separation principle through precise molecular structure design. The specific method comprises the following steps: a preparation method of a low-temperature-resistant waterproof moisture-permeable polyurethane adhesive comprises the following steps: Step one, mixing diisocyanate and polycarbonate polyol in a solvent for reaction, and adding amino silicone oil for reaction to obtain a first amino-terminated prepolymer for standby, wherein the first amino-terminated prepolymer is shown in the following structural formula 1: Structural formula 1, wherein R' is a molecular chain connecting two-NCO groups, R1 is a chain segment of poly 1, 6-hexanediol diphenyl carbonate, and R2 is a chain segment of polydimethylsiloxane; step two, mixing diisocyanate and polyether polyol in a solvent for reaction to obtain an isocyanate-terminated prepolymer for standby, wherein the isocyanate-terminated prepolymer is shown in the following structural formula 2: Structural formula 2; Step three, mixing and reacting the first amino-terminated prepolymer and the isocyanate-terminated prepolymer in a solvent to obtain a second amino-terminated prepolymer solution; and step four, mixing the second amino-terminated prepolymer solution with a polyisocyanate c