Single-sided adhesive processing agent, preparation method and application thereof

Abstract

The application belongs to the technical field of adhesives, and particularly relates to a single-sided adhesive processing agent and a preparation method and application thereof. The preparation method of the single-sided adhesive processing agent comprises mixing an alkenyl-terminated polyurethane solution with a double-end hydrogen-containing siloxane and a solvent, adding a silicon-hydrogen addition catalyst to react, and adding a cocatalyst, an inhibitor and a solvent after the reaction is completed to obtain the single-sided adhesive processing agent. When the single-sided adhesive processing agent is brushed on the surface of a shoe material containing double bonds, the double bonds on the surface of the shoe material are close to the silicon-hydrogen bonds, and under the combined catalysis of the silicon-hydrogen addition catalyst and the cocatalyst, the silicon-hydrogen addition reaction can continuously occur, the double bonds in the shoe material and the silicon-hydrogen bonds of the single-sided adhesive processing agent are combined through a chemical bond, and a stable bonding is formed.

Description

Technical Field

[0001] This invention belongs to the field of adhesive technology, specifically relating to a single-sided adhesive treatment agent, its preparation method, and its application. Background Technology

[0002] The footwear industry achieves bonding between the sole and upper by uniformly applying a polyurethane adhesive to pre-treated soles and uppers, allowing the adhesive to activate, and then bonding the two together. However, due to the low polarity of footwear materials and the potential use of processing aids such as release agents and finishing agents, compatibility with polyurethane adhesives can be poor. To address this, the industry typically pre-treats the footwear materials. Pre-treatment involves two steps: mechanical sanding and applying a treatment agent. First, mechanical sanding roughens the surface of the footwear material and removes surface contaminants, improving the wetting and spreading ability of the polyurethane adhesive on the substrate and its mechanical bonding ability. Then, a treatment agent is applied: a solvent is used to clean the surface of the footwear material, or a special compound is used to alter the surface polarity, thereby improving the bonding effect. However, conventional treatment agents cannot be stored stably for long periods. Therefore, during bonding, the appropriate treatment agent must be applied separately to the sanded sole and upper, dried, and then the polyurethane adhesive is applied. Therefore, at least two people are needed to apply the treatment agent and two people to apply the polyurethane adhesive on a single production line, resulting in high labor costs.

[0003] Chinese invention patent CN105266279A discloses a method for single-sided adhesive bonding in shoe manufacturing. This method utilizes a two-in-one treatment agent, which is a mixture of reinforcing agent and adhesive. This agent is directly brushed onto the bonding area of ​​the shoe upper, requiring only single-sided adhesive bonding to achieve adhesion to the sole. This reduces manual gluing steps, shortening the shoe manufacturing process and saving labor. However, the reinforcing agent used is a conventional treatment agent. After mixing the reinforcing agent with adhesive and brushing it onto the shoe material surface, some areas of the shoe material are covered by adhesive without any treatment effect. The treatment agent cannot effectively contact these areas, thus failing to achieve the purpose of treating the shoe material surface. This may result in insufficient treatment of the shoe material, leading to low bonding strength between the shoe material and the adhesive. Furthermore, due to the significant difference in polarity between the reinforcing agent and adhesive, they cannot be stored for long periods and must be prepared and used immediately, which is not conducive to factory assembly line production and affects product quality stability. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a single-sided adhesive treatment agent, its preparation method and application, which only requires single-sided adhesive application to complete the bonding of the sole and the upper.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a method for preparing a single-sided adhesive treatment agent, comprising the following steps:

[0006] S1: Polyester diol, small molecule diol and perfluoropolyether diol are mixed, and then diisocyanate and polyurethane catalyst are added for the first reaction; after the first reaction is completed, solvent, small molecule diamine and small molecule polyamine are added for the second reaction; after the second reaction is completed, alkenyl functional monomer is added for the third reaction; after the third reaction is completed, acetylacetone metal compound is added to obtain alkenyl-terminated polyurethane solution.

[0007] S2: The alkenyl-terminated polyurethane solution obtained in S1 is mixed with a double-ended hydrogen-containing siloxane and a solvent, and a hydrosilylation catalyst is added to carry out the reaction. After the reaction is completed, a co-catalyst, an inhibitor and a solvent are added to obtain a single-sided adhesive treatment agent.

[0008] Another technical solution adopted in this invention is: the single-sided adhesive treatment agent prepared by the above-mentioned method.

[0009] Another technical solution adopted in this invention is as follows: the application of the above-mentioned single-sided adhesive treatment agent in bonding shoe soles and shoe uppers includes the following steps: the shoe upper is coated with the treatment agent and adhesive in sequence, the shoe sole is coated with only the single-sided adhesive treatment agent, and the shoe sole and shoe upper are bonded together.

[0010] The beneficial effects of this invention are as follows: The preparation method of the single-sided adhesive treatment agent of this invention involves first reacting diisocyanate with perfluoropolyether diol, polyester diol, small molecule diol, small molecule diamine, and small molecule polyamine under a polyurethane catalyst to obtain a fluorinated polyurethane prepolymer; then reacting the active hydrogen in the alkenyl functional monomer with the isocyanate group of the fluorinated polyurethane prepolymer to obtain an alkenyl-terminated polyurethane; then, under the catalysis of a hydrosilylation catalyst, the alkenyl-terminated polyurethane reacts with one end of a double-ended hydrogen-containing siloxane to obtain a silane-modified fluorinated polyurethane with silane-hydrogen bonds on the end side; finally, by adding a co-catalyst and a suitable amount of solvent to dissolve evenly, the single-sided adhesive treatment agent is obtained. When the single-sided adhesive treatment agent is brushed onto the surface of shoe materials containing double bonds, the double bonds on the surface of the shoe material are close to the silane-hydrogen bonds. Under the combined catalytic action of the hydrosilylation catalyst and the co-catalyst, a continuous hydrosilylation reaction can occur, chemically bonding the double bonds in the shoe material and the silane-hydrogen bonds in the single-sided adhesive treatment agent to form a stable bond. Attached Figure Description

[0011] Figure 1 The image shown is the infrared spectrum of the single-sided adhesive treatment agent P1 according to Embodiment 1 of the present invention. Detailed Implementation

[0012] To explain in detail the technical content, objectives, and effects of the present invention, the following description is provided in conjunction with the embodiments and accompanying drawings.

[0013] A method for preparing a single-sided adhesive treatment agent includes the following steps:

[0014] S1: Polyester diol, small molecule diol and perfluoropolyether diol are mixed, and then diisocyanate and polyurethane catalyst are added for the first reaction; after the first reaction is completed, solvent, small molecule diamine and small molecule polyamine are added for the second reaction; after the second reaction is completed, alkenyl functional monomer is added for the third reaction; after the third reaction is completed, acetylacetone metal compound is added to obtain alkenyl-terminated polyurethane solution.

[0015] S2: The alkenyl-terminated polyurethane solution obtained in S1 is mixed with a double-ended hydrogen-containing siloxane and a solvent, and a hydrosilylation catalyst is added to carry out the reaction. After the reaction is completed, a co-catalyst, an inhibitor and a solvent are added to obtain a single-sided adhesive treatment agent.

[0016] As can be seen from the above description, the beneficial effects of the present invention are as follows: In the preparation method of the single-sided adhesive treatment agent of the present invention, in step S1, diisocyanate is first reacted with perfluoropolyether diol, polyester diol, small molecule diol, small molecule diamine and small molecule polyamine under a polyurethane catalyst to obtain a fluorinated polyurethane prepolymer. The low surface tension of the fluorinated polyether segments in the perfluoropolyether diol promotes the good adhesion of the effective components of the single-sided adhesive treatment agent to the surface of various substrates, thereby forming excellent spreading on the surface of the shoe sole substrate and providing conditions for hydrosilylation reaction. The small molecule diamine and small molecule diol act as chain extenders to increase the molecular weight of the polymer. The small molecule polyamine reacts with diisocyanate to form a star-shaped or multi-branched structure, which can improve the cohesive force of the polymer in the single-sided adhesive treatment agent system and ensure good compatibility between the solid components of the single-sided adhesive treatment agent after drying and conventional waterborne polyurethane adhesives, resulting in a strong bonding effect.

[0017] The active hydrogen in the alkenyl functional monomer is then reacted with the isocyanate group of the fluorinated polyurethane prepolymer to obtain alkenyl-terminated polyurethane. The addition of acetylacetone metal compound to the alkenyl-terminated polyurethane can relieve the toxicity of the polyurethane catalyst to the hydrosilylation catalyst, avoid hydrosilylation catalyst poisoning, and ensure the efficiency of the hydrosilylation catalyst.

[0018] In step S2, under the catalysis of the hydrosilylation catalyst, most of the hydrogen silane bonds at one end of the double-ended hydrogen-containing siloxanes quantitatively form stable Si-C chemical bonds with the double bonds of the alkenyl-terminated polyurethane, while the hydrogen silane bonds at the other end are retained, resulting in silane-modified fluorinated polyurethane with hydrogen silane bonds at both ends; a small portion of the hydrogen silane bonds at both ends form stable Si-C chemical bonds with the double bonds of the alkenyl-terminated polyurethane, playing a chain extension role and improving the cohesive force of the single-sided adhesive treatment agent.

[0019] Finally, by adding a co-catalyst, an inhibitor, and a solvent and dissolving them evenly, a single-sided adhesive treatment agent is obtained. The inhibitor suppresses the catalytic effect of the hydrosilylation catalyst in the solution, making the solution stable and easily volatilizing out of the system along with the solvent after application. Under the combined action of the co-catalyst, the hydrosilylation catalyst rapidly reacts with the double bonds in the shoe material to form a strong bond.

[0020] Furthermore, the specific steps of the first reaction are as follows: add diisocyanate at 60-65°C, then raise the temperature to 75-85°C and add polyurethane catalyst, and keep the reaction at this temperature for 2-5 hours.

[0021] Furthermore, the specific steps of the second reaction are as follows: add solvent, small molecule diamine and small molecule polyamine at 20-30℃, then raise the temperature to 50-60℃ and react for 1-2 hours.

[0022] As can be seen from the above description, adding the solvent at a lower temperature avoids the solvent evaporation affecting the system measurement.

[0023] Furthermore, the specific steps of the third reaction are as follows: add the alkenyl functional monomer at 20-30°C, then raise the temperature to 50-60°C within 1 hour, and react for 8-12 hours.

[0024] Furthermore, the acetylacetone metal compound is added to the reaction solution at 20–30°C.

[0025] Furthermore, the moisture content of the polyester diol, small molecule diol and perfluoropolyether diol in S1 is 0.05 to 0.1 wt%.

[0026] Further, by weight, the raw materials in S1 include 60-300 parts polyester diol, 2.7-10.2 parts small molecule diol, 85-187 parts perfluoropolyether diol, 37.7-79.5 parts diisocyanate, 0.08-0.12 parts polyurethane catalyst, 300-1200 parts solvent, 1.48-3.99 parts small molecule diamine, 0.85-2.06 parts small molecule polyamine, 0.93-7.65 parts alkenyl functional monomer and 2-3 parts acetylacetone metal compound.

[0027] As can be seen from the above description, the present invention needs to retain the NH bond reaction between the highly reactive NCO group and the alkenyl functional monomer, so small molecule diols, small molecule diamines and small molecule polyamines cannot be in excess.

[0028] Furthermore, the perfluoropolyether diol is a double-hydroxyl-terminated polyoxyethylene perfluoropolyether.

[0029] Further, the polyester diol is at least one of polycaprolactone diol, polypentyl adipate diol, poly-1,4-butanediol adipate diol, poly-1,6-hexanediol adipate diol, and polycarbonate diol, with an average molecular weight of 500 to 3000 Da.

[0030] Furthermore, the small molecule diol is any one of 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol.

[0031] Further, the diisocyanate is at least one of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0032] Furthermore, the small molecule diamine is any one of ethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,3-propanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, and 1,5-pentanediamine.

[0033] Furthermore, the small molecule polyamine is any one of divinyltriamine, triethylenetetramine, and tetraethylenepentamine.

[0034] Furthermore, the solvent is at least one of dimethyl carbonate, diethyl carbonate, and polymethoxydimethyl ether (pure DMM-2).

[0035] Polyoxymethylene dimethyl ether (pure DMM-2), the structural formula of DMM-2 is CH3OCH2OCH2OCH3.

[0036] Furthermore, the water content of the solvent is ≤0.05wt%.

[0037] Furthermore, the acetylacetone metal compound is either an aluminum acetylacetone solution or a gallium acetylacetone solution.

[0038] Furthermore, the method for preparing the aluminum acetylacetonate solution is as follows: a 2 wt% solution of aluminum acetylacetonate is prepared by dissolving aluminum acetylacetonate in dry dimethyl carbonate; the method for preparing the gallium acetylacetonate solution is as follows: a 2 wt% solution of gallium acetylacetonate is prepared by dissolving gallium acetylacetonate in dry dimethyl carbonate.

[0039] Furthermore, the polyurethane catalyst is an organic bismuth catalyst. Preferably, the polyurethane catalyst is DY-20 from Shanghai Deyin Chemical Co., Ltd., or [other catalyst] from Kaiyin Chemical Co., Ltd. 8108 and Any one of 8106.

[0040] Furthermore, the alkenyl functional monomer is at least one of 1-allylhydantoin and diallyl isocyanurate.

[0041] As can be seen from the above description, the selection of alkenyl functional monomers containing carbon and nitrogen heterocycles can promote adhesion and improve cohesive strength. After polymerization modification, the adhesion of the single-sided adhesive treatment agent to the surface of the shoe material can be enhanced, and the cohesive force of the single-sided adhesive treatment agent can be enhanced.

[0042] Further, the specific steps of S2 are as follows: the alkenyl-terminated polyurethane solution obtained in S1, the double-terminated hydrogen-containing siloxane and the solvent are mixed, the temperature is raised to 50-60°C, a hydrosilylation catalyst is added and the reaction is carried out for 3-5 hours. After the reaction is completed, the temperature is lowered to 20-30°C, and then a co-catalyst, an inhibitor and a solvent are added to obtain the single-sided adhesive treatment agent.

[0043] Furthermore, by weight, the raw materials in S2 include 0.87 to 17.9 parts of bihydrosiloxane, 250 to 850 parts of solvent, 1 to 2 parts of hydrosilylation catalyst, 1 to 2 parts of co-catalyst, and 5 to 7 parts of inhibitor.

[0044] As can be seen from the above description, the addition of an excessive amount of double-ended hydrogen-containing siloxanes in this invention results in most of the hydrogen-silicon bonds at one end of the double-ended hydrogen-containing siloxanes forming stable Si-C chemical bonds with the double bonds of the alkenyl-terminated polyurethane, while the hydrogen-silicon bonds at the other end are retained, thus obtaining silane-modified fluorinated polyurethane with hydrogen-silicon bonds on both ends; a small portion of the hydrogen-silicon bonds at both ends of the double-ended hydrogen-containing siloxanes form stable Si-C chemical bonds with the double bonds of the alkenyl-terminated polyurethane, playing a chain-extending role and improving the cohesive force of the single-sided adhesive treatment agent.

[0045] Furthermore, the solid content of the single-sided adhesive treatment agent is 20-25 wt%.

[0046] As can be seen from the above description, the present invention adjusts the solid content of the single-sided adhesive treatment agent by adding a solvent, so as to adjust the viscosity of the single-sided adhesive treatment agent to a suitable level.

[0047] Furthermore, the dihydrosiloxane is at least one of 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane.

[0048] Furthermore, the hydrosilylation catalyst is a solution of tris(triphenylphosphine)rhodium(I) chloride;

[0049] The method for preparing tri(triphenylphosphine) rhodium chloride (I) solution is as follows: a 1 wt% solution of tri(triphenylphosphine) rhodium chloride (I) is dissolved in dry dimethyl carbonate.

[0050] Furthermore, the co-catalyst is a solution of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene;

[0051] The method for preparing (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene solution is as follows: a 2wt% solution of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene is prepared by dissolving it in dry dimethyl carbonate.

[0052] Furthermore, the inhibitor is a mixed solution of trichloroethylene and perchloroethylene prepared in a weight ratio of 2:3.

[0053] Another technical solution adopted in this invention is: the single-sided adhesive treatment agent prepared by the above-mentioned method.

[0054] As described above, the effective component of the single-sided adhesive treatment agent of the present invention is silane-modified fluorinated polyurethane. Its molecular structure contains highly active silane-hydrogen bonds, which can undergo silane-hydrogen addition reaction with the double bonds in the shoe sole substrate at room temperature under the action of a silane-hydrogen addition catalyst to form chemical bonds, thereby achieving the effect of treating the shoe sole. The silane-modified fluorinated polyurethane contains perfluoropolyether segments and carbon-nitrogen heterocyclic compounds, has low surface tension, and strong adhesion to the shoe sole substrate. The silane-modified fluorinated polyurethane has strong cohesion and good affinity with polyurethane adhesives, and can be used as an adhesive.

[0055] Another technical solution adopted in this invention is as follows: the application of the above-mentioned single-sided adhesive treatment agent in bonding shoe soles and shoe uppers includes the following steps: the shoe upper is coated with the treatment agent and adhesive in sequence, the shoe sole is coated with only the single-sided adhesive treatment agent, and the shoe sole and shoe upper are bonded together.

[0056] As described above, when the single-sided adhesive treatment agent of this invention is brushed onto the surface of shoe materials containing double bonds, the double bonds on the surface of the shoe material are close to the silane-hydrogen bonds. Under the combined catalytic action of the hydrosilylation catalyst and the co-catalyst, a continuous hydrosilylation reaction can occur, chemically binding the double bonds in the shoe material and the silane-hydrogen bonds of the single-sided adhesive treatment agent to form a stable bond with good adhesion. This single-sided adhesive treatment agent can achieve the purpose of treating the substrate and forming an adhesive film with only one application to the shoe sole substrate, which can save manpower in shoe production; the bonded material can be sealed and stored in a cool, dry place for 6 months without significant decline in treatment effect, meeting the requirements of shoe factories.

[0057] Embodiment 1 of the present invention is a method for preparing a single-sided adhesive treatment agent, comprising the following steps:

[0058] S1: 46.7g of poly(1,4-butanediol adipate) diol with an average molecular weight of 500 Da, 13.3g of poly(1,4-butanediol adipate) diol with an average molecular weight of 2000 Da, 4.5g of 1,4-butanediol, and 170g of Flu E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to a reactor and heated to 110°C. The moisture content of the material was reduced to 0.05 wt% by vacuuming. The temperature was then lowered to 60°C, and 50.4 g of hexamethylene diisocyanate was added. The temperature was raised to 75°C, and 0.08 g of DY-20 from Shanghai Deyin Chemical Co., Ltd. was added. The reaction was maintained at this temperature for 5 hours. The temperature was then lowered to 20°C, and 400 g of dimethyl carbonate, 1.76 g of N-ethylethylenediamine, and 1.14 g of tetraethylenepentamine were added. The temperature was raised to 50°C, and the reaction was maintained for 2 hours. The temperature was then lowered to 20°C, and 4.18 g of 1-allyl hydantoin was added. The temperature was raised to 50°C within 1 hour, and the reaction was maintained for 12 hours. The temperature was then lowered to 20°C, and 2 g of a 2 wt% aluminum acetylacetonate dimethyl carbonate solution was added to obtain an alkenyl-terminated polyurethane solution.

[0059] S2: The alkenyl-terminated polyurethane solution obtained in S1, 3.9 g of 1,1,3,3-tetramethyldisiloxane and 400 g of dimethyl carbonate were added to a reaction vessel, heated to 55°C, and 1 g of dimethyl carbonate solution with a content of 1 wt% of tris(triphenylphosphine)rhodium(I) was added. The reaction was carried out for 4 hours. Then the temperature was lowered to 30°C, and 1 g of dimethyl carbonate solution with a content of 2 wt% of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene, 2 g of trichloroethylene, 3 g of perchloroethylene and an appropriate amount of dimethyl carbonate were added. The solid content was adjusted to 25 wt% to obtain single-sided adhesive treatment agent P1.

[0060] The infrared spectrum of single-sided adhesive treatment agent P1 is as follows: Figure 1 As shown. Figure 1 Medium, 2800-3000cm -1 1436~1450cm -1 These are characteristic absorption peaks for methyl and methylene groups; 2135 cm⁻¹ -1 It is a characteristic absorption peak of Si-H; 1735 cm⁻¹ -1 These are characteristic absorption peaks of the ester group in acrylates; 1100–1300 cm⁻¹ -1 These are characteristic absorption peaks of the CF and COC bonds in perfluoropolyether. These characteristic peaks indicate that the single-sided adhesive treatment agent P1 was prepared in Example 1. According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of the single-sided adhesive treatment agent P1 was 0.0123 mol / kg, slightly lower than the theoretical value of 0.0136 mol / kg, which also proves that the single-sided adhesive treatment agent P1 contains silicon-hydrogen bonds.

[0061] Embodiment 2 of the present invention is: a method for preparing a single-sided adhesive treatment agent, the steps of which are as follows:

[0062] S1: 200g of polycaprolactone diol with an average molecular weight of 3000 Da, 66.7g of polycarbonate diol with an average molecular weight of 2000 Da, 4.72g of 1,6-hexanediol, and 136g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to the reactor, and the temperature was raised to 120°C. The moisture content of the material was reduced to 0.1 wt% by vacuuming. Then, the temperature was lowered to 65°C, and 38 g of 4,4'-dicyclohexylmethane diisocyanate and 25.5 g of isophorone diisocyanate were added. The temperature was raised to 85°C, and 0.12 g of polyurethane catalyst from Kaiyin Chemical Co., Ltd. was added. 8108, keep the reaction at this temperature for 2 hours; then cool to 30°C, add 900g diethyl carbonate, 1.48g 1,2-propanediamine and 0.85g diallyltriamine, heat to 60°C, and react for 1 hour; then cool to 25°C, add 3.02g diallyl isocyanurate, heat to 60°C within 1 hour, and react for 8 hours; then cool to 30°C, add 3g dimethyl carbonate solution with an aluminum acetylacetonate content of 2wt%, to obtain an alkenyl-terminated polyurethane solution;

[0063] S2: The alkenyl-terminated polyurethane solution obtained in S1, 6g of 1,1,3,3,5,5-hexamethyltrisiloxane and 600g of DMM2 were added to a reaction vessel, heated to 60℃, and 2g of dimethyl carbonate solution with a content of 1wt% of tris(triphenylphosphine)rhodium(I) was added. The reaction was carried out for 3 hours. Then the temperature was lowered to 30℃, and 1g of dimethyl carbonate solution with a content of 2wt% of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene, 2.4g of trichloroethylene, 3.6g of perchloroethylene and an appropriate amount of diethyl carbonate were added. The solid content was adjusted to 24wt% to obtain single-sided adhesive treatment agent P2.

[0064] According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of single-sided adhesive treatment agent P2 is 0.0071 mol / kg.

[0065] Embodiment 3 of the present invention is a method for preparing a single-sided adhesive treatment agent, comprising the following steps:

[0066] S1: 180g of poly(neopentyl adipate) glycol with an average molecular weight of 3000 Da, 120g of poly(1,6-hexanediol adipate) glycol with an average molecular weight of 3000 Da, 2.7g of 1,4-butanediol, and 136g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to the reactor, and the temperature was raised to 115°C. The moisture content of the material was reduced to 0.08 wt% by vacuuming. Then, the temperature was lowered to 62°C, and 60.6 g of isophorone diisocyanate was added. The temperature was then raised to 77°C, and 0.09 g of polyurethane catalyst from Kaiyin Chemical Co., Ltd. was added. 8106 was reacted at this temperature for 3.5 hours; then the temperature was lowered to 20°C, and 1200g of DMM2, 1.5g of ethylenediamine, and 1.46g of triethylenetetramine were added. The temperature was then raised to 55°C and reacted for 1.5 hours; then the temperature was lowered to 25°C, and 3.65g of diallyl isocyanurate and 4g of 1-allyl hydantoin were added. The temperature was then raised to 60°C within 1 hour and reacted for 8 hours; then the temperature was lowered to 25°C, and 2g of a 2wt% gallium acetylacetonate dimethyl carbonate solution was added to obtain an alkenyl-terminated polyurethane solution.

[0067] S2: The alkenyl-terminated polyurethane solution obtained in S1, 17.9g of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, and 800g of dimethyl carbonate were added to a reaction vessel. The mixture was heated to 50°C, and 2g of a dimethyl carbonate solution with a rhodium(triphenylphosphine) chloride (I) content of 1wt% was added. The reaction was carried out for 5 hours. Then the mixture was cooled to 20°C, and 1g of a dimethyl carbonate solution with a (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene content of 2wt%, 2.2g of trichloroethylene, 3.3g of perchloroethylene, and an appropriate amount of dimethyl carbonate were added. The solid content was adjusted to 20wt% to obtain single-sided adhesive treatment agent P3.

[0068] According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of single-sided adhesive treatment agent P3 is 0.0125 mol / kg.

[0069] Embodiment four of the present invention is: a method for preparing a single-sided adhesive treatment agent, the steps of which are as follows:

[0070] S1: 100g of polycarbonate diol with an average molecular weight of 1000 Da, 5.84g of 1,8-octanediol, and 144.5g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to a reactor and heated to 110°C. The moisture content of the material was reduced to 0.05 wt% by vacuuming. The temperature was then lowered to 63°C, and 79.5 g of 4,4'-dicyclohexylmethane diisocyanate was added. The temperature was raised to 75°C, and 0.1 g of DY-20 from Shanghai Deyin Chemical Co., Ltd. was added. The reaction was maintained at this temperature for 5 hours. The temperature was then lowered to 20°C, and 400 g of diethyl carbonate, 400 g of DMM2, 2.6 g of 1,2-propanediamine, and 2.06 g of divinyltriamine were added. The temperature was raised to 55°C, and the reaction was maintained for 1.5 hours. The temperature was then lowered to 25°C, and 3.82 g of 1-allyl hydantoin was added. The temperature was raised to 55°C within one hour, and the reaction was maintained for 10 hours. The temperature was then lowered to 23°C, and 2 g of a 2 wt% gallium acetylacetonate dimethyl carbonate solution was added to obtain an alkenyl-terminated polyurethane solution.

[0071] S2: The alkenyl-terminated polyurethane solution obtained in S1, 3.6 g of 1,1,3,3-tetramethyldisiloxane, and 350 g of diethyl carbonate were added to a reaction vessel, heated to 60°C, and 1.5 g of dimethyl carbonate solution with a content of 1 wt% of tris(triphenylphosphine)rhodium(I) was added. The reaction was carried out for 5 hours. Then the temperature was lowered to 25°C, and 1 g of dimethyl carbonate solution with a content of 2 wt% of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene, 2.4 g of trichloroethylene, 3.6 g of perchloroethylene, and an appropriate amount of dimethyl carbonate were added. The solid content was adjusted to 22 wt% to obtain single-sided adhesive treatment agent P4.

[0072] According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of single-sided adhesive treatment agent P4 is 0.0086 mol / kg.

[0073] Embodiment 5 of the present invention is a method for preparing a single-sided adhesive treatment agent, comprising the following steps:

[0074] S1: 100g of polycaprolactone diol with an average molecular weight of 2000 Da, 125g of polypentyl adipate diol with an average molecular weight of 2500 Da, 10.2g of 1,8-octanediol, and 187g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to a reactor and heated to 120°C. The moisture content of the material was reduced to 0.08 wt% by vacuuming. The temperature was then lowered to 60°C, and 57 g of isophorone diisocyanate and 15.2 g of hexamethylene diisocyanate were added. The temperature was raised to 85°C, and 0.08 g of DY-20 from Shanghai Deyin Chemical Co., Ltd. was added. The reaction was maintained at this temperature for 2 hours. The temperature was then lowered to 30°C, and 1100 g of diethyl carbonate, 2.75 g of 1,5-pentanediamine, and 2 g of divinyltriamine were added. The temperature was raised to 55°C, and the reaction was maintained for 2 hours. The temperature was then lowered to 26°C, and 4.65 g of diallyl isocyanurate was added. The temperature was raised to 50°C within one hour, and the reaction was maintained for 12 hours. The temperature was then lowered to 25°C, and 3 g of a 2 wt% gallium acetylacetonate dimethyl carbonate solution was added. The washing liquid was combined with the filtered transparent solution to obtain an alkenyl-terminated polyurethane solution.

[0075] S2: The alkenyl-terminated polyurethane solution obtained in S1, 8.85g of 1,1,3,3,5,5-hexamethyltrisiloxane, and 500g of diethyl carbonate were added to a reaction vessel. The temperature was raised to 57°C, and 2g of dimethyl carbonate solution with a content of 1wt% of tris(triphenylphosphine)rhodium(I) was added. The reaction was carried out for 5 hours. Then the temperature was lowered to 20°C, and 1.5g of dimethyl carbonate solution with a content of 2wt% of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene, 2.8g of trichloroethylene, 4.2g of perchloroethylene, and an appropriate amount of DMM2 were added. The solid content was adjusted to 24wt% to obtain single-sided adhesive treatment agent P5.

[0076] According to the method of "HG / T 4658-2014 Determination of active hydrogen content in hydrogen-containing silicone oil for textile dyeing and finishing auxiliaries", the Si-H content of single-sided adhesive treatment agent P5 is 0.0094 mol / kg.

[0077] Embodiment six of the present invention is: a method for preparing a single-sided adhesive treatment agent, the steps of which are as follows:

[0078] S1: 120g of poly(1,6-hexanediol adipate) diol with an average molecular weight of 2000 Da, 90g of poly(neopentyl adipate) diol with an average molecular weight of 2250 Da, 5.4g of 1,4-butanediol, and 153g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to the reactor, and the temperature was raised to 120°C. The moisture content of the material was reduced to 0.1 wt% by vacuuming. Then, the temperature was lowered to 65°C, and 53.76 g of hexamethylene diisocyanate was added. The temperature was then raised to 76°C, and 0.1 g of polyurethane catalyst from Kaiyin Chemical Co., Ltd. was added. 8106 was used to maintain the reaction temperature for 4 hours; then the temperature was lowered to 20°C, and 900g of dimethyl carbonate, 3.99g of 1,4-cyclohexanediamine and 1.9g of triethylenetetramine were added. The temperature was raised to 60°C and the reaction was carried out for 1 hour; then the temperature was lowered to 20°C, and 3.76g of diallyl isocyanurate was added. The temperature was raised to 53°C within 1 hour and the reaction was carried out for 11 hours; then the temperature was lowered to 20°C, and 2.5g of a dimethyl carbonate solution with a gallium acetylacetonate content of 2wt% was added to obtain an alkenyl-terminated polyurethane solution.

[0079] S2: The alkenyl-terminated polyurethane solution obtained in S1, 5.97 g of 1,1,3,3-tetramethyldisiloxane and 550 g of DMM2 were added to a reaction vessel, heated to 55°C, and 2 g of dimethyl carbonate solution with a content of 1 wt% of tris(triphenylphosphine)rhodium(I) was added. The reaction was carried out for 4 hours. Then the temperature was lowered to 25°C, and 2 g of dimethyl carbonate solution with a content of 2 wt% of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene, 2 g of trichloroethylene, 3 g of perchloroethylene and an appropriate amount of DMM2 were added. The solid content was adjusted to 21 wt% to obtain single-sided adhesive treatment agent P6.

[0080] According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of single-sided adhesive treatment agent P6 is 0.0113 mol / kg.

[0081] Embodiment 7 of the present invention is a method for preparing a single-sided adhesive treatment agent, comprising the following steps:

[0082] S1: 200g of poly(neopentyl adipate) glycol with an average molecular weight of 2000 Da, 4.72g of 1,6-hexanediol, and 85g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to the reactor, and the temperature was raised to 116°C. The moisture content of the material was reduced to 0.05 wt% by vacuuming. Then, the temperature was lowered to 63°C, and 37.7 g of hexamethylene diisocyanate was added. The temperature was then raised to 81°C, and 0.11 g of polyurethane catalyst from Kaiyin Chemical Co., Ltd. was added. 8108, keep the reaction at this temperature for 3 hours; then cool to 20-30℃, add 300g diethyl carbonate, 200g DMM2, 1.74g 1,6-hexanediamine and 1.16g triethylenetetramine, heat to 57℃, and react for 1.5 hours; then cool to 25℃, add 0.93g 1-allylhydantoin, heat to 57℃ within 1 hour, and react for 9 hours; then cool to 20℃, add 2g of dimethyl carbonate solution with a gallium acetylacetonate content of 2wt%, to obtain an alkenyl-terminated polyurethane solution;

[0083] S2: The alkenyl-terminated polyurethane solution obtained in S1, 0.87 g of 1,1,3,3-tetramethyldisiloxane, and 400 g of DMM2 were added to a reaction vessel, heated to 53°C, and 2 g of dimethyl carbonate solution with a content of 1 wt% of tris(triphenylphosphine)rhodium(I) was added. The reaction was carried out for 5 hours. Then the temperature was lowered to 20°C, and 1.5 g of dimethyl carbonate solution with a content of 2 wt% of (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene, 2.64 g of trichloroethylene, 3.96 g of perchloroethylene, and an appropriate amount of dimethyl carbonate were added. The solid content was adjusted to 25 wt% to obtain single-sided adhesive treatment agent P7.

[0084] According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of single-sided adhesive treatment agent P7 is 0.0025 mol / kg.

[0085] Embodiment 8 of the present invention is a method for preparing a single-sided adhesive treatment agent, comprising the following steps:

[0086] S1: 45g of poly(neopentyl adipate) glycol with an average molecular weight of 500 Da, 20g of poly(1,4-butanediol adipate) glycol with an average molecular weight of 2000 Da, 4.5g of 1,4-butanediol, and 68g of... E10-H (hydroxyl-terminated polyoxyethylene perfluoropolyether) was added to a reactor and heated to 115°C. The moisture content of the material was reduced to 0.06 wt% by vacuuming. The temperature was then lowered to 60°C, and 39.3 g of hexamethylene diisocyanate was added. The temperature was raised to 75°C, and 0.08 g of DY-20 from Shanghai Deyin Chemical Co., Ltd. was added. The reaction was maintained at this temperature for 5 hours. The temperature was then lowered to 20°C, and 300 g of dimethyl carbonate, 1.65 g of N-ethylethylenediamine, and 0.51 g of diethylenetriamine were added. The temperature was raised to 50°C, and the reaction was maintained for 2 hours. The temperature was then lowered to 20°C, and 3.5 g of 1-allyl hydantoin was added. The temperature was raised to 56°C within 1 hour, and the reaction was maintained for 10 hours. The temperature was then lowered to 20°C, and 2.5 g of a 2 wt% aluminum acetylacetonate solution of dimethyl carbonate was added to obtain an alkenyl-terminated polyurethane solution.

[0087] S2: The alkenyl-terminated polyurethane solution obtained in S1, 5.2 g of 1,1,3,3,5,5-hexamethyltrisiloxane, and 250 g of dimethyl carbonate were added to a reaction vessel. The temperature was raised to 50°C, and 1 g of dimethyl carbonate solution with a tris(triphenylphosphine) rhodium chloride (I) content of 1 wt% was added. The reaction was carried out for 4 hours. Then the temperature was lowered to 30°C, and 1 g of dimethyl carbonate solution with a (R)-(+)-2-diphenylphosphine-2'-methoxy-1,1'-binaphthylene content of 2 wt% was added, along with 2.4 g of trichloroethylene, 3.6 g of perchloroethylene, and an appropriate amount of dimethyl carbonate. The solid content was adjusted to 25 wt% to obtain single-sided adhesive treatment agent P8.

[0088] According to the method in "HG / T 4658-2014 Determination of Active Hydrogen Content in Hydrogen-Containing Silicone Oil for Textile Dyeing and Finishing Auxiliaries", the Si-H content of single-sided adhesive treatment agent P8 is 0.0165 mol / kg.

[0089] Example 9 of this invention is a single-sided adhesive treatment agent prepared using the preparation method of Example 1.

[0090] The tenth embodiment used in this invention is as follows:

[0091] The application of single-sided adhesive treatment agent in bonding shoe soles and uppers involves the following steps: roughening the area of ​​the shoe sole containing unsaturated double bonds to be bonded, removing debris, applying the single-sided adhesive treatment agent of the embodiment to the shoe sole, and drying it; applying a conventional nylon treatment agent to the shoe upper and drying it, then applying an adhesive and drying it, pressing the shoe sole and the upper together, and freezing it to complete the bonding.

[0092] The performance of single-sided adhesive treatment agents P1 to P8 obtained in Examples 1 and 8 of this invention was tested:

[0093] A conventional rubber treatment agent (HXL-1026N rubber treatment agent from Fujian Huaxia Lan New Material Technology Co., Ltd., with 1 wt% isocyanate added before use and dissolved evenly) was selected and designated as single-sided adhesive treatment agent P9. P9 should be used within 4 hours. A two-component waterborne polyurethane adhesive HXL-8101 and curing agent GHJ-101 from Fujian Huaxia Lan New Material Technology Co., Ltd. were mixed evenly at a weight ratio of 100:5 to form adhesive S1. This adhesive should be used within 4 hours.

[0094] Preparation of shoe samples T1-T10: Rubber soles were roughened and pre-treated at the bonding area to remove debris. Ten pairs were grouped together, and each group was pre-treated with single-sided adhesive treatment agents P1-P9. Ninety pairs of nylon flyknit uppers were all treated with nylon treatment agent HXL-043N from Fujian Huaxia Lan New Material Technology Co., Ltd. All soles and uppers were then placed in a 70℃ oven for 3 minutes until the treatment agent was completely dry. Adhesive S1 was evenly applied to all uppers, but not to the soles. The glued uppers were then placed in a 70℃ oven for 5 minutes. Once the liquid film was dry and activated, the uppers were immediately removed, and the soles and uppers were bonded together. Immediately afterward, a pressure of 1.0 MPa was applied for 12 seconds. After releasing the pressure, the uppers were placed in a freezer for 1 minute to obtain shoe samples T1-T9. Prepare shoe sample T10 (conventional double-sided gluing process). The only difference between T10 and T9 is that the sole is also coated with adhesive S1.

[0095] The obtained shoe samples T1 to T10 were placed in an environment with a temperature of 23±2℃ and a relative humidity of 50±5% for 24 hours to equilibrate. Five pairs of each of the equilibrated shoe samples T1 to T10 were taken and the bonding strength was tested according to GB 532-2008. The test was performed 10 times in parallel for each sample, and the average value was taken. The results are shown in Table 1.

[0096] Five pairs of shoes from T1 to T10 were taken and tested for damp heat resistance according to GB / T 30779-2014: The rubber strips were placed in a constant temperature and humidity chamber at 70±2℃ and 95±5% relative humidity for 72 hours, and then placed in an environment at 23±2℃ and 50±5% relative humidity for 24 hours to equilibrate. The adhesive strength was then tested according to GB / T 532-2008, and the average value was taken. The results are shown in Table 1.

[0097] Table 1

[0098]

[0099] As shown in Table 1, the shoe samples (T1-T8) obtained by using the single-sided adhesive treatment agents P1-P8 of this invention in combination with single-sided adhesive application exhibit high bonding strength between the sole and upper, comparable to the effect of shoe sample (T10) which simultaneously applies conventional double-sided treatment agent P9 and adhesive S1, both achieving material damage. This indicates that the single-sided adhesive treatment agent of this invention has excellent treatment effect, achieving the effect of double-sided adhesive application without applying adhesive to the sole, thus meeting the usage standards. However, shoe sample (T9) with only conventional treatment agent P9 applied to the sole without water-based polyurethane adhesive S1 exhibits low bonding strength. During the test, the adhesive layer adhered entirely to the upper, leaving the sole untouched and the sole material undamaged. This is clearly due to the poor bonding effect between the sole without water-based polyurethane adhesive S1 and the upper using it. Its average bonding strength is far below the national standard requirement of 3.5 N / mm, potentially leading to a very high defect rate in actual production and severely impacting production efficiency.

[0100] The results of the damp heat resistance test in Table 1 show that the single-sided adhesive treatment agents P1 to P8 of the present invention have a bonding strength retention rate of 70% to 90% after the test, which is close to the effect of conventional double-sided adhesive products and meets the standards for use in shoe factories. However, T9 has too low bonding strength, and the sole and upper of the shoe completely delaminate, which does not meet the standards for use.

[0101] The single-sided adhesive treatment agents P1, P7 and P8 of the present invention were sealed and stored in high-density polyethylene bottles. After being placed at 35°C in the dark for 6 months, they were compared with new batches of single-sided adhesive treatment agents P1, P7 and P8 according to the single-sided adhesive shoe manufacturing method in Table 1. Shoe samples T11 to T16 were obtained, and their performance comparison test results are shown in Table 2.

[0102] Table 2

[0103] shoe pattern shoe sole treatment agent Shoe sole rubber sample shoe upper rubber sample Average bond strength, N / mm T11 P1 - S1 8.21 - Shoe sole cracked T12 P1 (stored for 6 months) - S1 7.38 - Shoe sole cracked T13 P7 - S1 5.59 - Slight crack in the sole T14 P7 (stored for 6 months) - S1 4.57 - Slight crack in the sole T15 P8 - S1 10.54 - Sole crack T16 P8 (stored for 6 months) - S1 8.75 - Sole crack

[0104] As shown in Table 2, the single-sided adhesive treatment agent of this invention retains more than 80% of its performance after 6 months of storage, and the sole materials all show cracks, indicating that its bonding effect is excellent and meets the national standard requirement of ≥3.5 N / mm bonding strength. The single-sided adhesive treatment agent of this invention can be used for more than 6 months under normal conditions when stored in an inert container in a sealed, light-proof container at room temperature, meeting the standards for use in shoe factories.

[0105] In summary, the single-sided adhesive treatment agent, its preparation method, and its application provided by this invention have the following advantages:

[0106] 1. During preparation, the low surface tension of the fluorinated polyether segments in the perfluoropolyether diol is utilized to promote the good adhesion of the effective components of the single-sided adhesive to the surface of various substrates, providing conditions for hydrosilylation reaction.

[0107] 2. Small molecule polyamines were used in the formulation design. The reaction of small molecule polyamines with isocyanates forms a star-shaped or multi-branched structure, which can improve the cohesive force of the polymer in the single-sided adhesive treatment system and obtain a strong bonding effect.

[0108] 3. Adding acetylacetone metal compounds can relieve the toxicity of polyurethane catalysts to hydrosilylation catalysts and ensure the efficiency of hydrosilylation catalysts.

[0109] 4. Under the catalysis of hydrosilylation catalyst, most of the hydrogen-silicon bonds at one end of the double-ended hydrogen-containing siloxanes quantitatively form stable Si-C chemical bonds with the double bonds of the alkenyl-terminated polyurethane, while the hydrogen-silicon bonds at the other end are retained; a small portion of the hydrogen-silicon bonds at both ends of the double-ended hydrogen-containing siloxanes form stable Si-C chemical bonds with the double bonds of the alkenyl-terminated polyurethane, which plays a chain extension role and improves the cohesive force of the single-sided adhesive treatment agent.

[0110] 5. Add inhibitors. Inhibitors suppress the catalytic effect of hydrosilylation catalysts in solution, making the solution stable and easy to evaporate from the system with the solvent after construction. Under the combined action of co-catalysts, hydrosilylation catalysts quickly react with double bonds in shoe materials to form a strong bond.

[0111] 6. When the single-sided adhesive treatment agent is brushed onto the surface of shoe materials containing double bonds, the double bonds on the surface of the shoe material are close to the silane-hydrogen bonds. Under the combined catalytic action of the hydrosilylation catalyst and the co-catalyst, the hydrosilylation reaction can continue to occur, and the double bonds in the shoe material and the silane-hydrogen bonds of the single-sided adhesive treatment agent are chemically bonded to form a stable bond.

[0112] 7. This single-sided adhesive treatment agent can achieve single-sided adhesive bonding of shoe uppers and soles containing unsaturated double bonds, greatly reducing labor costs.

[0113] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification and drawings, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for preparing a single-sided adhesive treatment agent, characterized in that, Includes the following steps: S1: Polyester diol, small molecule diol and perfluoropolyether diol are mixed, and then diisocyanate and polyurethane catalyst are added for the first reaction; after the first reaction is completed, solvent, small molecule diamine and small molecule polyamine are added for the second reaction; after the second reaction is completed, alkenyl functional monomer is added for the third reaction; after the third reaction is completed, acetylacetone metal compound is added to obtain alkenyl-terminated polyurethane solution. By weight, the raw materials in S1 include 60-300 parts polyester diol, 2.7-10.2 parts small molecule diol, 85-187 parts perfluoropolyether diol, 37.7-79.5 parts diisocyanate, 0.08-0.12 parts polyurethane catalyst, 300-1200 parts solvent, 1.48-3.99 parts small molecule diamine, 0.85-2.06 parts small molecule polyamine, 0.93-7.65 parts alkenyl functional monomer and 2-3 parts acetylacetone metal compound; S2: The alkenyl-terminated polyurethane solution obtained in S1 is mixed with a double-ended hydrogen-containing siloxane and a solvent, and a hydrosilylation catalyst is added to carry out the reaction. After the reaction is completed, a co-catalyst, an inhibitor and a solvent are added to obtain a single-sided adhesive treatment agent. By weight, the raw materials in S2 include 0.87 to 17.9 parts of bihydrosiloxane, 250 to 850 parts of solvent, 1 to 2 parts of hydrosilylation catalyst, 1 to 2 parts of co-catalyst and 5 to 7 parts of inhibitor.

2. The method for preparing the single-sided adhesive treatment agent according to claim 1, characterized in that, The specific steps of the first reaction are as follows: add diisocyanate at 60~65℃, then raise the temperature to 75~85℃ and add polyurethane catalyst, and keep the temperature for 2~5 hours.

3. The method for preparing the single-sided adhesive treatment agent according to claim 1, characterized in that, The specific steps of the second reaction are as follows: add solvent, small molecule diamine and small molecule polyamine at 20~30℃, then raise the temperature to 50~60℃ and react for 1~2 hours.

4. The method for preparing the single-sided adhesive treatment agent according to claim 1, characterized in that, The specific steps of the third reaction are as follows: add the alkenyl functional monomer at 20~30℃, then raise the temperature to 50~60℃ within 1 hour, and react for 8~12 hours.

5. The method for preparing the single-sided adhesive treatment agent according to claim 1, characterized in that, The moisture content of the polyester diol, small molecule diol and perfluoropolyether diol in S1 is 0.05~0.1wt%.

6. The method for preparing the single-sided adhesive treatment agent according to claim 1, characterized in that, The specific steps of S2 are as follows: the alkenyl-terminated polyurethane solution obtained in S1, the double-terminated hydrogen-containing siloxane and the solvent are mixed, the temperature is raised to 50~60℃, a hydrosilylation catalyst is added and the reaction is carried out for 3~5 hours. After the reaction is completed, the temperature is lowered to 20~30℃, and then a co-catalyst, an inhibitor and a solvent are added to obtain a single-sided adhesive treatment agent.

7. A single-sided adhesive treatment agent prepared by the preparation method of any one of claims 1-6.

8. The application of the single-sided adhesive treatment agent as described in claim 7 in bonding shoe soles and shoe uppers, characterized in that, Includes the following steps: The upper is coated with a treatment agent and an adhesive in sequence, while the sole is coated with only a single-sided adhesive treatment agent, and the sole and upper are then bonded together.

Images