A hydrolysis-resistant water-based adhesive for shoe-making and its processing technology

Abstract

The present invention relates to the technical field of adhesives, and specifically to a hydrolysis-resistant water-based adhesive for shoe-making and its processing technology. The present invention uses a water-based polyurethane emulsion and a polysiloxane grafted with a benzene ring to prepare a modified water-based polyurethane. An epoxy resin and the modified water-based polyurethane are used, and various additives are added to prepare a hydrolysis-resistant water-based adhesive for shoe-making. The polysiloxane grafted with a benzene ring contains a benzene ring, and the addition of the benzene ring can improve the hydrolysis resistance and tensile strength of the hydrolysis-resistant water-based adhesive for shoe-making. The polysiloxane grafted with a benzene ring also contains fluorine elements on the benzene ring, enhancing the hydrophobic property of the hydrolysis-resistant water-based adhesive. The hydrolysis-resistant water-based adhesive for shoe-making prepared by the present invention has good hydrolysis resistance and mechanical properties, meeting the application in the shoe-making field.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and particularly to a water-based adhesive resistant to hydrolysis for shoe-making and its processing technology. Background Art

[0002] The upper and the sole are usually bonded by an adhesive. Due to the influence of sweat and water vapor generated by the user's long-term walking activities, the glue will be eroded, resulting in the sole cracking and falling off. In order to enhance the service life of the shoes, the adhesive needs to have good hydrolysis resistance and corrosion resistance. Usually, polyurethane emulsion is used as the adhesive for shoes in the industry, but the hydrolysis resistance of polyurethane emulsion is not strong and its mechanical properties are not good. Therefore, it is crucial to enhance the hydrolysis resistance of the water-based adhesive for shoe-making.

[0003] In order to solve the above problems and improve the hydrolysis resistance of the water-based adhesive for shoe-making, the present invention provides a water-based adhesive resistant to hydrolysis for shoe-making and its processing technology. Summary of the Invention

[0004] The purpose of the present invention is to provide a water-based adhesive resistant to hydrolysis for shoe-making and its processing technology to solve the problems raised in the above background art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A processing technology of a water-based adhesive resistant to hydrolysis for shoe-making, comprising the following steps:

[0007] Step 1: Take succinic anhydride and toluene, stir evenly to obtain a succinic anhydride solution; take fluorinated polysiloxane, add toluene and pyridine, stir evenly, dropwise add the succinic anhydride solution, react for 5 - 7 h, add p-toluenesulfonic acid, raise the temperature to 110 - 120 °C, react for 6 - 8 h, dry, add triethylamine and N, N-dimethylformamide, then dropwise add benzoyl chloride, raise the temperature to 60 - 65 °C, stir for 3 - 4 h, cool to 25 - 30 °C, wash, filter and dry to obtain polysiloxane grafted with a benzene ring;

[0008] Step 2: Take a water-based polyurethane emulsion and polysiloxane grafted with a benzene ring, stir evenly to obtain a modified water-based polyurethane;

[0009] Step 3: Take epoxy resin, modified water-based polyurethane and deionized water, stir for 15 - 20 min, add an antifoaming agent, a crosslinking agent, a dispersing agent and a rheology aid, continue to stir for 10 - 15 min to obtain a resin mixture, add diisocyanate, and continue to stir for 5 - 10 min to obtain a water-based adhesive resistant to hydrolysis for shoe-making.

[0010] Preferably, in step two, the mass ratio of the aqueous polyurethane emulsion to the polysiloxane grafted with a benzene ring is 100:(15 - 20).

[0011] Preferably, the hydrolysis-resistant aqueous adhesive for shoes comprises the following components by weight: 55 - 75 parts of modified aqueous polyurethane, 20 - 30 parts of epoxy resin, 15 - 17 parts of cross-linking agent, 0.1 - 0.2 part of defoaming agent, 0.1 - 0.2 part of rheology aid, 0.1 - 0.2 part of dispersant, 70 - 80 parts of deionized water, and 8 - 10 parts of diisocyanate.

[0012] Preferably, the preparation method of the fluorinated polysiloxane is as follows: Trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and tetramethyltetravinylcyclotetrasiloxane are introduced into nitrogen, stirred at 85 - 88 °C for 20 - 40 min, heated to 105 - 110 °C, tetramethylammonium hydroxide and capping agent H2O are added, and the reaction continues for 2.5 - 3.5 h. Then it is further heated to 145 - 150 °C and kept warm for 2 - 3 h, and decompressed for 2 - 4 h to obtain the fluorinated polysiloxane.

[0013] Preferably, the preparation method of the aqueous polyurethane emulsion is as follows: Take polyether polyol, add 1,6 - hexamethylene diisocyanate and isophorone diisocyanate, and while stirring, heat up to 80 - 85 °C, react for 50 - 70 min, add acetone and diethanolamide oleate, continue to react for 50 - 70 min, add dimethylglyoxime, continue to react for 50 - 70 min, keep the reaction temperature at 80 - 85 °C, react for 6 - 7 h, cool down to 55 - 60 °C, add triethylamine, react for 30 - 40 min, add deionized water, and stir for emulsification to obtain the aqueous polyurethane emulsion.

[0014] Preferably, the cross-linking agent is carbodiimide; the defoaming agent is silicone oil; the rheology aid is AKN - 7020.

[0015] Preferably, the dispersant is any one or more of polyethylene wax and calcium stearate.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0017] (1) Firstly, the present invention prepares a fluorinated polysiloxane by adding trifluoropropyltrimethylcyclotrisiloxane. The introduction of fluorine elements can enhance the hydrophobic property of the aqueous adhesive. Then, a large number of hydroxyl groups on the fluorinated polysiloxane are modified by adding benzoyl chloride, thereby introducing a benzene ring onto the fluorinated polysiloxane. The benzene ring is a rigid structure, and the introduction of the benzene ring can enhance the water resistance and tensile strength of the aqueous adhesive.

[0018] (2) The present invention uses an aqueous polyurethane emulsion and a polysiloxane grafted with a benzene ring to prepare a modified aqueous polyurethane. When preparing the aqueous polyurethane emulsion, a large amount of 1,6 - hexamethylene diisocyanate and isophorone diisocyanate are added. A large number of isocyanate groups in the aqueous polyurethane emulsion can react with a large number of hydroxyl groups on the polysiloxane grafted with a benzene ring. By controlling the mass ratio of the aqueous polyurethane emulsion to the polysiloxane grafted with a benzene ring to be 100:(15 - 20), the stability of the aqueous polyurethane emulsion is improved, and the hydrolysis resistance of the aqueous adhesive is enhanced. Detailed implementation mode

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1

[0021] Step 1: Preparation of aqueous polyurethane emulsion:

[0022] Take 30 g of polyether polyol, add 20 g of 1,6 - hexamethylene diisocyanate and 3 g of isophorone diisocyanate, and heat up to 83 °C with stirring. React for 65 min, add 30 mL of acetone and 2 g of diethanolamide oleate, continue to react for 65 min, add 6 g of dimethylglyoxime, continue to react for 65 min, keep the reaction temperature at 83 °C, react for 6.5 h, cool down to 57 °C, add 2 g of triethylamine, react for 35 min, add 100 mL of deionized water, and stir for emulsification to obtain an aqueous polyurethane emulsion.

[0023] The average molecular weight of the polyether polyol is 1000, purchased from Xuchuan Chemical Industry (Suzhou) Co., Ltd.

[0024] Step 2: Preparation of fluorinated polysiloxane:

[0025] Pass 55 g of trifluoropropyltrimethylcyclotrisiloxane, 24.5 g of octamethylcyclotetrasiloxane, and 28 g of tetramethyltetravinylcyclotetrasiloxane into nitrogen, stir at 83 °C for 30 min, heat up to 107 °C, add 0.013 g of tetramethylammonium hydroxide and 0.07 g of capping agent H2O, continue to react for 3 h, continue to heat up to 147 °C and keep warm for 2.5 h, and reduce pressure for 3 h to obtain fluorinated polysiloxane.

[0026] Step 3: Preparation of polysiloxane grafted with a benzene ring:

[0027] Take 10 g of succinic anhydride and 10 mL of toluene, stir evenly to obtain a succinic anhydride solution; take 13 g of fluorinated polysiloxane, add 20 mL of toluene and 0.5 g of pyridine, stir evenly, dropwise add the succinic anhydride solution, react for 6 h, add 0.1 g of p-toluenesulfonic acid, raise the temperature to 115 °C, react for 7 h, dry, add 1 mL of triethylamine and 30 mL of N,N-dimethylformamide, then dropwise add 30 mL of benzoyl chloride, raise the temperature to 63 °C, stir for 3.5 h, cool to 27 °C, wash, filter and dry to obtain polysiloxane grafted with benzene ring.

[0028] Step 4: Preparation of modified waterborne polyurethane:

[0029] Take the waterborne polyurethane emulsion and the polysiloxane grafted with benzene ring, stir evenly to obtain the modified waterborne polyurethane.

[0030] The mass ratio of the waterborne polyurethane emulsion to the polysiloxane grafted with benzene ring is 100:17.

[0031] Step 5: Preparation of hydrolysis-resistant waterborne adhesive for shoe-making:

[0032] Take epoxy resin, modified waterborne polyurethane and deionized water, stir for 17 min, add defoamer, crosslinking agent, dispersant polyethylene wax and rheology aid, continue to stir for 13 min to obtain a resin mixture, add diisocyanate, continue to stir for 7 min to obtain a hydrolysis-resistant waterborne adhesive for shoe-making.

[0033] Epoxy resin: CYD-128 type, purchased from Baling Petrochemical Company, Sinopec Group.

[0034] The hydrolysis-resistant waterborne adhesive for shoe-making includes the following components by weight:

[0035] 70 parts of modified waterborne polyurethane, 25 parts of epoxy resin, 16 parts of crosslinking agent, 0.1 part of defoamer, 0.1 part of rheology aid, 0.1 part of dispersant polyethylene wax, 70 parts of deionized water, 8 parts of diisocyanate.

[0036] Example 2

[0037] Step 1: Preparation of waterborne polyurethane emulsion:

[0038] Take 30 g of polyether polyol, add 20 g of 1,6-hexamethylene diisocyanate and 3 g of isophorone diisocyanate, stir and heat up to 80 °C, react for 50 min, add 30 mL of acetone and 2 g of oleic acid diethanolamide, continue to react for 50 min, add 6 g of butanedione dioxime, continue to react for 50 min, keep the reaction temperature at 80 °C, react for 6 h, cool down to 55 °C, add 2 g of triethylamine, react for 30 min, add 100 mL of deionized water, stir and emulsify to obtain the waterborne polyurethane emulsion.

[0039] The average molecular weight of the polyether polyol is 1000, and it is purchased from Asahi Kasei Chemicals (Suzhou) Co., Ltd.

[0040] Step 2: Preparation of fluorinated polysiloxane:

[0041] 55 g of trifluoropropyltrimethylcyclotrisiloxane, 24.5 g of octamethylcyclotetrasiloxane, and 28 g of tetramethyltetravinylcyclotetrasiloxane were introduced, and nitrogen was passed through. The mixture was stirred at 85 °C for 20 min, then heated to 105 °C, 0.013 g of tetramethylammonium hydroxide and 0.07 g of end-capping agent H2O were added, and the reaction continued for 2.5 h. Then it was further heated to 145 °C and kept warm for 2 h, and depressurized for 2 h to obtain fluorinated polysiloxane.

[0042] Step 3: Preparation of polysiloxane grafted with benzene ring:

[0043] 10 g of succinic anhydride and 10 mL of toluene were taken and stirred evenly to obtain a succinic anhydride solution; 13 g of fluorinated polysiloxane, 20 mL of toluene, and 0.5 g of pyridine were added and stirred evenly. The succinic anhydride solution was added dropwise, and the reaction was carried out for 5 h. 0.1 g of p-toluenesulfonic acid was added, and the temperature was raised to 110 °C, and the reaction continued for 6 h. After drying, 1 mL of triethylamine and 30 mL of N,N-dimethylformamide were added, then 30 mL of benzoyl chloride was added dropwise, the temperature was raised to 60 °C, and the mixture was stirred for 3 h. After cooling to 25 °C, it was washed, filtered, and dried to obtain polysiloxane grafted with benzene ring.

[0044] Step 4: Preparation of modified waterborne polyurethane:

[0045] Waterborne polyurethane emulsion and polysiloxane grafted with benzene ring were taken and stirred evenly to obtain modified waterborne polyurethane.

[0046] The mass ratio of the waterborne polyurethane emulsion to the polysiloxane grafted with benzene ring is 100:15.

[0047] Step 5: Preparation of hydrolysis-resistant waterborne adhesive for shoe-making:

[0048] Epoxy resin, modified waterborne polyurethane, and deionized water were taken and stirred for 15 min, then defoamer, cross-linking agent, dispersant calcium stearate, and rheology aid were added, and stirring continued for 10 min to obtain a resin mixture. Diisocyanate was added, and stirring continued for 5 min to obtain a hydrolysis-resistant waterborne adhesive for shoe-making.

[0049] Epoxy resin: CYD-128 type, purchased from Baling Petrochemical Company, Sinopec Group.

[0050] The hydrolysis-resistant waterborne adhesive for shoe-making comprises the following components by weight:

[0051] 55 parts of modified aqueous polyurethane, 20 parts of epoxy resin, 15 parts of crosslinking agent, 0.1 part of defoaming agent, 0.1 part of rheological aid, 0.1 part of dispersant calcium stearate, 70 parts of deionized water, 8 parts of diisocyanate.

[0052] Example 3

[0053] Step 1: Preparation of aqueous polyurethane emulsion:

[0054] Take 30 g of polyether polyol, add 20 g of 1,6 - hexamethylene diisocyanate and 3 g of isophorone diisocyanate, heat up to 85°C while stirring, react for 70 min, add 30 mL of acetone and 2 g of diethanolamide oleate, continue to react for 70 min, add 6 g of dimethylglyoxime, continue to react for 70 min, keep the reaction temperature at 85°C, react for 7 h, cool down to 60°C, add 2 g of triethylamine, react for 40 min, add 100 mL of deionized water, stir and emulsify to obtain an aqueous polyurethane emulsion.

[0055] The polyether polyol with an average molecular weight of 1000 was purchased from Xuchuan Chemical Industry (Suzhou) Co., Ltd.

[0056] Step 2: Preparation of fluorinated polysiloxane:

[0057] Charge 55 g of trifluoropropyltrimethylcyclotrisiloxane, 24.5 g of octamethylcyclotetrasiloxane, and 28 g of tetramethyltetravinylcyclotetrasiloxane, introduce nitrogen, stir at 88°C for 40 min, heat up to 110°C, add 0.013 g of tetramethylammonium hydroxide and 0.07 g of capping agent H2O, continue to react for 3.5 h, continue to heat up to 150°C and keep warm for 3 h, reduce pressure for 4 h to obtain fluorinated polysiloxane.

[0058] Step 3: Preparation of polysiloxane grafted with benzene ring:

[0059] Take 10 g of succinic anhydride and 10 mL of toluene, stir evenly to obtain a succinic anhydride solution; take 13 g of fluorinated polysiloxane, add 20 mL of toluene and 0.5 g of pyridine, stir evenly, dropwise add the succinic anhydride solution, react for 7 h, add 0.1 g of p - toluenesulfonic acid, heat up to 120°C, react for 8 h, dry, add 1 mL of triethylamine and 30 mL of N,N - dimethylformamide, then dropwise add 30 mL of benzoyl chloride, heat up to 65°C, stir for 4 h, cool to 30°C, wash, filter, and dry to obtain polysiloxane grafted with benzene ring.

[0060] Step 4: Preparation of modified aqueous polyurethane:

[0061] Take the aqueous polyurethane emulsion and the polysiloxane grafted with benzene ring, stir evenly to obtain modified aqueous polyurethane.

[0062] The mass ratio of the aqueous polyurethane emulsion to the polysiloxane grafted with a benzene ring is 100:20.

[0063] Step Five: Preparation of the hydrolysis-resistant aqueous adhesive for shoe-making:

[0064] Take epoxy resin, modified aqueous polyurethane, and deionized water, stir for 20 min, add an antifoaming agent, a cross-linking agent, a dispersant polyethylene wax, and a rheology aid, continue stirring for 15 min to obtain a resin mixture, add diisocyanate, and continue stirring for 10 min to obtain a hydrolysis-resistant aqueous adhesive for shoe-making.

[0065] Epoxy resin: CYD-128 type, purchased from Baling Petrochemical Company, Sinopec Group.

[0066] The hydrolysis-resistant aqueous adhesive for shoe-making comprises the following components by weight:

[0067] 75 parts of modified aqueous polyurethane, 30 parts of epoxy resin, 17 parts of cross-linking agent, 0.2 part of antifoaming agent, 0.2 part of rheology aid, 0.2 part of dispersant polyethylene wax, 80 parts of deionized water, 10 parts of diisocyanate.

[0068] Example 4: Do not introduce a benzene ring onto the fluorinated polysiloxane, and the rest is the same as in Example 1.

[0069] Step One: Preparation of the aqueous polyurethane emulsion:

[0070] Take 30 g of polyether polyol, add 20 g of 1,6-hexamethylene diisocyanate and 3 g of isophorone diisocyanate, heat up to 83 °C while stirring, react for 65 min, add 30 mL of acetone and 2 g of diethanolamide oleate, continue reacting for 65 min, add 6 g of dimethylglyoxime, continue reacting for 65 min, keep the reaction temperature at 83 °C, react for 6.5 h, cool down to 57 °C, add 2 g of triethylamine, react for 35 min, add 100 mL of deionized water, and stir for emulsification to obtain an aqueous polyurethane emulsion.

[0071] The average molecular weight of the polyether polyol is 1000, purchased from Xuchuan Chemical Industry (Suzhou) Co., Ltd.

[0072] Step Two: Preparation of the fluorinated polysiloxane:

[0073] Pass 55 g of trifluoropropyltrimethylcyclotrisiloxane, 24.5 g of octamethylcyclotetrasiloxane, and 28 g of tetramethyltetravinylcyclotetrasiloxane into nitrogen, stir at 83 °C for 30 min, heat up to 107 °C, add 0.013 g of tetramethylammonium hydroxide and 0.07 g of capping agent H2O, continue reacting for 3 h, continue heating up to 147 °C and keep warm for 2.5 h, and reduce the pressure for 3 h to obtain the fluorinated polysiloxane.

[0074] Step 3: Preparation of modified aqueous polyurethane:

[0075] Take the aqueous polyurethane emulsion and fluorinated polysiloxane, stir evenly to obtain the modified aqueous polyurethane.

[0076] The mass ratio of the aqueous polyurethane emulsion to the fluorinated polysiloxane is 100:17.

[0077] Step 4: Preparation of hydrolysis-resistant aqueous adhesive for shoe-making:

[0078] Take epoxy resin, modified aqueous polyurethane, and deionized water, stir for 17 min, add defoamer, crosslinking agent, dispersant polyethylene wax, and rheological aid, continue stirring for 13 min to obtain a resin mixture, add diisocyanate, and continue stirring for 7 min to obtain a hydrolysis-resistant aqueous adhesive for shoe-making.

[0079] Epoxy resin: CYD-128 type, purchased from Baling Petrochemical Company, Sinopec Group.

[0080] The hydrolysis-resistant aqueous adhesive for shoe-making includes the following components by weight:

[0081] 70 parts of modified aqueous polyurethane, 25 parts of epoxy resin, 16 parts of crosslinking agent, 0.1 part of defoamer, 0.1 part of rheological aid, 0.1 part of dispersant polyethylene wax, 70 parts of deionized water, 8 parts of diisocyanate.

[0082] Example 5: Control the mass ratio of the aqueous polyurethane emulsion to the polysiloxane grafted with benzene ring to be 100:10.

[0083] Step 1: Preparation of aqueous polyurethane emulsion:

[0084] Take 30 g of polyether polyol, add 20 g of 1,6-hexamethylene diisocyanate and 3 g of isophorone diisocyanate, heat up to 83 °C while stirring, react for 65 min, add 30 mL of acetone and 2 g of oleic acid diethanolamide, continue to react for 65 min, add 6 g of dimethylglyoxime, continue to react for 65 min, keep the reaction temperature at 83 °C, react for 6.5 h, cool down to 57 °C, add 2 g of triethylamine, react for 35 min, add 100 mL of deionized water, stir and emulsify to obtain the aqueous polyurethane emulsion.

[0085] The average molecular weight of the polyether polyol is 1000, purchased from Xuchuan Chemical Industry (Suzhou) Co., Ltd.

[0086] Step 2: Preparation of fluorinated polysiloxane:

[0087] 55 g of trifluoropropyltrimethylcyclotrisiloxane, 24.5 g of octamethylcyclotetrasiloxane, and 28 g of tetramethyltetravinylcyclotetrasiloxane were introduced with nitrogen, stirred at 83 °C for 30 min, heated to 107 °C, 0.013 g of tetramethylammonium hydroxide and 0.07 g of capping agent H2O were added, and the reaction continued for 3 h. Then it was further heated to 147 °C and kept warm for 2.5 h, and depressurized for 3 h to obtain fluorinated polysiloxane.

[0088] Step 3: Preparation of polysiloxane grafted with benzene ring:

[0089] 10 g of succinic anhydride and 10 mL of toluene were taken and stirred evenly to obtain a succinic anhydride solution; 13 g of fluorinated polysiloxane, 20 mL of toluene, and 0.5 g of pyridine were added, stirred evenly, the succinic anhydride solution was added dropwise, and the reaction was carried out for 6 h. 0.1 g of p-toluenesulfonic acid was added, heated to 115 °C, and the reaction was carried out for 7 h. After drying, 1 mL of triethylamine and 30 mL of N,N-dimethylformamide were added, and then 30 mL of benzoyl chloride was added dropwise, heated to 63 °C, stirred for 3.5 h, cooled to 27 °C, washed, filtered, and dried to obtain polysiloxane grafted with benzene ring.

[0090] Step 4: Preparation of modified waterborne polyurethane:

[0091] The waterborne polyurethane emulsion and the polysiloxane grafted with benzene ring were taken and stirred evenly to obtain modified waterborne polyurethane.

[0092] The mass ratio of the waterborne polyurethane emulsion to the polysiloxane grafted with benzene ring is 100:10.

[0093] Step 5: Preparation of hydrolysis-resistant waterborne adhesive for shoemaking:

[0094] Epoxy resin, modified waterborne polyurethane, and deionized water were taken and stirred for 17 min, defoaming agent, crosslinking agent, dispersant polyethylene wax, and rheology aid were added, and stirring continued for 13 min to obtain a resin mixture. Diisocyanate was added, and stirring continued for 7 min to obtain a hydrolysis-resistant waterborne adhesive for shoemaking.

[0095] Epoxy resin: CYD-128 type, purchased from Baling Petrochemical Company, Sinopec Group.

[0096] The hydrolysis-resistant waterborne adhesive for shoemaking includes the following components by weight:

[0097] 70 parts of modified waterborne polyurethane, 25 parts of epoxy resin, 16 parts of crosslinking agent, 0.1 part of defoaming agent, 0.1 part of rheology aid, 0.1 part of dispersant polyethylene wax, 70 parts of deionized water, 8 parts of diisocyanate.

[0098] Experiment

[0099] The waterborne adhesives with hydrolysis resistance for shoe-making prepared in Examples 1 to 5 were coated on plastic sheets and dried at 60°C for 30 min. The change value of the tensile strength of the waterborne adhesives was tested according to GB / T 30779 to characterize the hydrothermal resistance of the waterborne adhesives. They were placed in an environment with a temperature of 75°C and a humidity of 95% for 14 days, and the change value of the tensile strength was tested; the tensile strength of the waterborne adhesives was tested according to GB / T 30779, and the obtained data are shown in the following table:

[0100] Damp heat resistance Tensile strength MPa Example 1 -1.1％ 2.04 Example 2 -1.3％ 2.02 Example 3 -1.1％ 2.07 Example 4 -16.4％ 1.62 Example 5 -8.7％ 1.77

[0101] Conclusion: It can be seen from the comparison of the data in the table that in Example 4, when no benzene ring is introduced onto the fluorinated polysiloxane, the hydrolysis resistance and tensile strength performance of the waterborne adhesives with hydrolysis resistance for shoe-making become much worse. In Example 5, when the mass ratio of the waterborne polyurethane emulsion to the polysiloxane grafted with a benzene ring is controlled to be 100:10, the hydrolysis resistance and tensile strength performance of the waterborne adhesives with hydrolysis resistance for shoe-making decrease. When the addition amount of the polysiloxane grafted with a benzene ring is relatively large and the mass ratio of the waterborne polyurethane emulsion to the polysiloxane grafted with a benzene ring is 100:(15 - 20), the tensile strength of the waterborne adhesives with hydrolysis resistance for shoe-making can reach 2 MPa. At this time, the introduction of the rigid benzene ring structure can enhance the mechanical properties of the waterborne adhesives. The change values of the tensile strength of the waterborne adhesives prepared in Examples 1 to 3 are also small, indicating that the waterborne adhesives have good hydrolysis resistance.

[0102] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A processing technology of a hydrolysis-resistant water-based adhesive for shoe-making, characterized in that: It includes the following steps: Step 1: Take succinic anhydride and toluene, stir evenly to obtain a succinic anhydride solution; take fluorinated polysiloxane, add toluene and pyridine, stir evenly, dropwise add the succinic anhydride solution, react for 5 - 7 h, add p-toluenesulfonic acid, heat up to 110 - 120 °C, react for 6 - 8 h, dry, add triethylamine and N,N-dimethylformamide, then dropwise add benzoyl chloride, heat up to 60 - 65 °C, stir for 3 - 4 h, cool to 25 - 30 °C, wash, filter and dry to obtain polysiloxane grafted with a benzene ring; Step 2: Take an aqueous polyurethane emulsion and polysiloxane grafted with a benzene ring, stir evenly to obtain a modified aqueous polyurethane; Step 3: Take epoxy resin, modified aqueous polyurethane and deionized water, stir for 15 - 20 min, add an antifoaming agent, a crosslinking agent, a dispersing agent and a rheology aid, continue to stir for 10 - 15 min to obtain a resin mixture, add diisocyanate, continue to stir for 5 - 10 min to obtain a hydrolysis-resistant aqueous adhesive for shoe-making; In Step 2, the mass ratio of the aqueous polyurethane emulsion to the polysiloxane grafted with a benzene ring is 100:(15 - 20); The hydrolysis-resistant aqueous adhesive for shoe-making includes the following components by weight: 55 - 75 parts of modified aqueous polyurethane, 20 - 30 parts of epoxy resin, 15 - 17 parts of crosslinking agent, 0.1 - 0.2 part of antifoaming agent, 0.1 - 0.2 part of rheology aid, 0.1 - 0.2 part of dispersing agent, 70 - 80 parts of deionized water, 8 - 10 parts of diisocyanate.

2. The processing technology of a hydrolysis-resistant water-based adhesive for shoe-making according to claim 1, characterized in that: The preparation method of the fluorinated polysiloxane is as follows: Feed trifluoropropyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane into nitrogen, stir at 85 - 88 °C for 20 - 40 min, heat up to 105 - 110 °C, add tetramethylammonium hydroxide and a capping agent H2O, continue to react for 2.5 - 3.5 h, continue to heat up to 145 - 150 °C and keep warm for 2 - 3 h, reduce pressure for 2 - 4 h to obtain fluorinated polysiloxane.

3. The processing technology of a hydrolysis-resistant water-based adhesive for shoe-making according to claim 1, characterized in that: The preparation method of the aqueous polyurethane emulsion is as follows: Take polyether polyol, add 1,6-hexamethylene diisocyanate and isophorone diisocyanate, heat up to 80 - 85 °C while stirring, react for 50 - 70 min, add acetone and dioleic acid diethanolamide, continue to react for 50 - 70 min, add dimethylglyoxime, continue to react for 50 - 70 min, keep the reaction temperature at 80 - 85 °C, react for 6 - 7 h, cool to 55 - 60 °C, add triethylamine, react for 30 - 40 min, add deionized water, stir and emulsify to obtain an aqueous polyurethane emulsion.

4. The processing technology of a hydrolysis-resistant water-based adhesive for shoe-making according to claim 1, characterized in that: The crosslinking agent is carbodiimide; the antifoaming agent is silicone oil; the rheology aid is AKN-7020.

5. The processing technology of a hydrolysis-resistant water-based adhesive for shoe-making according to claim 1, characterized in that: The dispersing agent is any one or more of polyethylene wax and calcium stearate.

6. A hydrolysis-resistant water-based adhesive for shoe-making obtained by processing according to the processing technology of a hydrolysis-resistant water-based adhesive for shoe-making described in any one of claims 1-5.