Preparation method of antibacterial waterproof adhesive and application in shoe materials

Abstract

The present invention relates to the technical field of adhesives, and discloses a preparation method of an antibacterial waterproof adhesive and its application in shoe materials, wherein component A comprises 100 parts by weight of polyether polyol, 19-25 parts by weight of diisocyanate, and 0.15-0.18 parts by weight of dibutyltin dilaurate; component B comprises 75-88 parts by weight of polyether polyol, 3-6 parts by weight of chain extender, 5-30 parts by weight of fluorine-containing quaternary ammonium salt antibacterial agent, and 12-20 parts by weight of dioctyl adipate; the fluorine-containing quaternary ammonium salt antibacterial agent of the present invention contains a strongly hydrophobic hexafluoroisopropylidene biphenyl structure, which is conducive to reducing the water absorption rate of the adhesive film, thereby improving water resistance and waterproof performance. In addition, the fluorine-containing quaternary ammonium salt antibacterial agent has good compatibility with the polyurethane adhesive, is evenly dispersed in the film matrix, and imparts excellent antibacterial properties to the adhesive.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to a preparation method of an antibacterial and waterproof adhesive and application of the adhesive in shoe materials. Background Art

[0002] Polyurethane adhesives have the advantages of good bonding performance, simple preparation method, and convenient construction. They are widely used in footwear, building materials, electronic appliances, and sports goods. Footwear mainly consists of uppers, soles, and adhesives. Footwear is prone to cracking when exposed to water during long-term wear, and is prone to breeding bacteria and mold in a humid environment. Therefore, it is necessary to improve the water resistance, waterproofness, antibacterial and mildew resistance of footwear adhesives.

[0003] Adding functional additives such as antibacterial agents to adhesives can give adhesives antibacterial, waterproof and other properties. However, the added additives may be incompatible with the matrix, which affects the peel strength, bonding performance and other properties of the adhesive. Patent CN116640546B discloses the use of aspartic acid, cellulose, tris (2-aminoethyl) amine, benzyl bromide and other raw materials to prepare hyperbranched quaternary ammonium salt modified cellulose aerogel, giving polyurethane adhesives good heat insulation, heat preservation, antibacterial and other properties. However, the quaternary ammonium salts of the invention, cellulose and other raw materials are hydrophilic substances, and adding them to polyurethane adhesives will affect their water resistance and waterproof properties. Summary of the invention

[0004] (1) The present invention solves the problem of poor waterproof and antibacterial properties of polyurethane adhesives.

[0005] (II) The technical solution of the present invention is: a method for preparing an antibacterial waterproof adhesive, comprising the following steps:

[0006] S1. Add isopropanol, 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate, and dimethylamino monomer in a mass ratio of 1:(0.65-0.72) to a flask equipped with a condenser reflux tube, heat to 80-85°C, stir and react for 18-36 hours, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a fluorine-containing quaternary ammonium salt antibacterial agent. The reaction formula is as follows:

[0007]

[0008] S2. Add 100 parts by weight of polyether polyol into a container, heat to 120°C and vacuum dehydrate for 2 hours, cool to 70-80°C, add 19-25 parts by weight of diisocyanate and 0.15-0.18 parts by weight of dibutyltin dilaurate, and stir to react for 2.5-3 hours in a nitrogen atmosphere to obtain component A; cool to room temperature, then add component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0009] The component B is composed of 75-88 parts by weight of polyether polyol, 3-6 parts by weight of chain extender, 5-30 parts by weight of fluorine-containing quaternary ammonium salt antibacterial agent, 12-20 parts by weight of dioctyl adipate, 0.8-1.2 parts by weight of defoamer and 0.12-0.16 parts by weight of dibutyltin dilaurate.

[0010] Furthermore, the diisocyanate is diphenylmethane-4,4'-diisocyanate or toluene-2,4-diisocyanate.

[0011] Furthermore, the chain extender is 1,4-butanediol, 1,6-hexanediol or trimethylolpropane.

[0012] Further, the preparation method of 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate is as follows: put a flask in an ice bath, add dichloromethane, hexafluorobisphenol A, triethylamine, and 4-chlorobutyryl chloride in a mass ratio of 1: (0.6-0.78): (0.84-1.08), remove the ice bath, stir and react at 20-35°C for 6-10h, distill under reduced pressure, wash with water, dry, dissolve the product in dichloromethane, and recrystallize to obtain 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate. The reaction formula is as follows:

[0013]

[0014] Furthermore, the preparation method of the dimethylamino monomer is as follows: add toluene, hexamethylene diisocyanate and 3-dimethylamino-1-propanol in a mass ratio of 1: (1.22-1.46) into a flask, heat to 70-85°C, stir and react for 5-8h, remove low boiling points by vacuum distillation, wash with petroleum ether, and dry to obtain the dimethylamino monomer. The reaction formula is as follows:

[0015]

[0016] Furthermore, the application of antibacterial and waterproof adhesives in shoe materials.

[0017] (III) The technical effect is as follows: the present invention utilizes 4,4'-(hexafluoroisopropyl)biphenyl chlorobutyrate and dimethylamino monomer to undergo quaternization reaction to obtain a fluorine-containing quaternary ammonium salt antibacterial agent; and then adds the fluorine-containing quaternary ammonium salt antibacterial agent to a two-component polyurethane adhesive. Since the molecular main chain of the antibacterial agent contains the same carbamate group as that of the polyurethane, the fluorine-containing quaternary ammonium salt antibacterial agent and the polyurethane have good interface compatibility, and have almost no adverse effects on the mechanical properties of the adhesive, such as the peel strength and Shore A hardness.

[0018] The fluorine-containing quaternary ammonium salt antibacterial agent of the present invention contains a highly hydrophobic hexafluoroisopropylidene biphenyl structure, which is beneficial to reducing the water absorption rate of the adhesive film, thereby improving the water resistance and waterproof performance. In addition, the fluorine-containing quaternary ammonium salt antibacterial agent has good compatibility with the polyurethane adhesive, is evenly dispersed in the film matrix, and gives the adhesive antibacterial properties, showing a high antibacterial rate against Candida albicans, Escherichia coli, and Staphylococcus aureus. DETAILED DESCRIPTION

[0019] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

[0020] Embodiment 1:

[0021] (1) Place a flask in an ice bath, add 70 mL of dichloromethane, 5 g of hexafluorobisphenol A, 3 g of triethylamine, and 4.2 g of 4-chlorobutyryl chloride, remove the ice bath, stir and react at 35°C for 7 h, distill under reduced pressure, wash with water, and dry. Dissolve the product in dichloromethane and recrystallize to obtain 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate.

[0022] (2) Add 50 mL of toluene, 3 g of hexamethylene diisocyanate, and 4.38 g of 3-dimethylamino-1-propanol into a flask, heat to 75°C, stir and react for 5 h, remove low boiling points by vacuum distillation, wash with petroleum ether, and dry to obtain a dimethylamino monomer.

[0023] (3) Add 70 mL of isopropanol, 6 g of 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate, and 4.32 g of bis(dimethylamino)monomer to a flask equipped with a condenser reflux tube, heat to 85°C, stir to react for 18 h, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a fluorine-containing quaternary ammonium salt antibacterial agent.

[0024] (4) Add 100 g of polyether polyol (model DL-1000) into a container, heat to 120°C and vacuum dehydrate for 2 h, cool to 80°C, add 25 g of diphenylmethane-4,4'-diisocyanate and 0.16 g of dibutyltin dilaurate, and stir to react for 2.5 h in a nitrogen atmosphere to obtain component A; cool to room temperature, then add 88 g of polyether polyol (model DL-1000), 4.7 g of chain extender 1,4-butanediol, 5 g of fluorine-containing quaternary ammonium salt antibacterial agent, 16 g of dioctyl adipate, 1.2 g of defoaming agent and 0.12 g of dibutyltin dilaurate as component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0025] Embodiment 2:

[0026] (1) Place a flask in an ice bath, add 70 mL of dichloromethane, 5 g of hexafluorobisphenol A, 3.9 g of triethylamine, and 4.7 g of 4-chlorobutyryl chloride, remove the ice bath, stir and react at 20°C for 10 h, distill under reduced pressure, wash with water, and dry. Dissolve the product in dichloromethane and recrystallize to obtain 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate.

[0027] (2) Add 50 mL of toluene, 3 g of hexamethylene diisocyanate, and 4.38 g of 3-dimethylamino-1-propanol into a flask, heat to 70°C, stir and react for 8 h, remove low boiling points by vacuum distillation, wash with petroleum ether, and dry to obtain a dimethylamino monomer.

[0028] (3) Add 80 mL of isopropanol, 6 g of 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate, and 3.9 g of bis(dimethylamino)monomer to a flask equipped with a condenser reflux tube, heat to 80°C, stir to react for 24 h, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a fluorine-containing quaternary ammonium salt antibacterial agent.

[0029] (4) Add 100 g of polyether polyol (model DL-1000) into a container, heat to 120°C and vacuum dehydrate for 2 h, cool to 80°C, add 19 g of toluene-2,4-diisocyanate and 0.15 g of dibutyltin dilaurate, and stir to react for 3 h in a nitrogen atmosphere to obtain component A; cool to room temperature, then add 86 g of polyether polyol (model DL-1000), 6 g of chain extender 1.6-hexanediol, 18 g of fluorine-containing quaternary ammonium salt antibacterial agent, 20 g of dioctyl adipate, 0.8 g of defoaming agent and 0.16 g of dibutyltin dilaurate as component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0030] Embodiment 3:

[0031] (1) Place a flask in an ice bath, add 80 mL of dichloromethane, 5 g of hexafluorobisphenol A, 3.9 g of triethylamine, and 5.4 g of 4-chlorobutyryl chloride, remove the ice bath, stir and react at 35°C for 6 h, distill under reduced pressure, wash with water, and dry. Dissolve the product in dichloromethane and recrystallize to obtain 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate.

[0032] (2) Add 50 mL of toluene, 3 g of hexamethylene diisocyanate, and 3.66 g of 3-dimethylamino-1-propanol into a flask, heat to 85°C, stir and react for 5 h, remove low boiling points by vacuum distillation, wash with petroleum ether, and dry to obtain a dimethylamino monomer.

[0033] (3) Add 70 mL of isopropanol, 6 g of 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate, and 3.9 g of bis(dimethylamino)monomer to a flask equipped with a condenser reflux tube, heat to 80°C, stir to react for 36 h, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a fluorine-containing quaternary ammonium salt antibacterial agent.

[0034] (4) Add 100 g of polyether polyol (model DL-1000) into a container, heat to 120°C and vacuum dehydrate for 2 h, cool to 70°C, add 19 g of toluene-2,4-diisocyanate and 0.18 g of dibutyltin dilaurate, and react under nitrogen atmosphere for 2.5 h to obtain component A; cool to room temperature, then add 75 g of polyether polyol (model DL-1000), 3 g of chain extender trimethylolpropane, 30 g of fluorine-containing quaternary ammonium salt antibacterial agent, 12 g of dioctyl adipate, 1.2 g of defoaming agent and 0.16 g of dibutyltin dilaurate as component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0035] Comparative Example 1:

[0036] (1) Add 100 g of polyether polyol (model DL-1000) into a container, heat to 120°C and vacuum dehydrate for 2 h, cool to 80°C, add 25 g of diphenylmethane-4,4'-diisocyanate and 0.16 g of dibutyltin dilaurate, and stir to react for 2.5 h in a nitrogen atmosphere to obtain component A; cool to room temperature, then add 88 g of polyether polyol (model DL-1000), 4.7 g of chain extender 1,4-butanediol, 16 g of dioctyl adipate, 1.2 g of defoamer and 0.12 g of dibutyltin dilaurate as component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0037] Comparative Example 2:

[0038] (1) Add 70 mL of isopropanol, 6 g of 1,10-dichlorodecane (CAS No. 2162-98-3) and 4.32 g of bis(dimethylamino) monomer into a flask equipped with a condenser reflux tube, heat to 85°C, stir to react for 18 h, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a quaternary ammonium salt antibacterial agent.

[0039] (2) Add 100 g of polyether polyol (model DL-1000) into a container, heat to 120°C and vacuum dehydrate for 2 h, cool to 80°C, add 25 g of diphenylmethane-4,4'-diisocyanate and 0.16 g of dibutyltin dilaurate, and stir to react for 2.5 h in a nitrogen atmosphere to obtain component A; cool to room temperature, then add 88 g of polyether polyol (model DL-1000), 4.7 g of chain extender 1,4-butanediol, 5 g of quaternary ammonium salt antibacterial agent, 16 g of dioctyl adipate, 1.2 g of defoaming agent and 0.12 g of dibutyltin dilaurate as component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0040] Comparative Example 3:

[0041] (1) Add 70 mL of isopropanol, 6 g of 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate, and 4.32 g of tetramethyl-1,4-butanediamine (CAS No. 111-51-3) into a flask equipped with a condenser reflux tube, heat to 85°C, stir to react for 18 hours, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a fluorine-containing quaternary ammonium salt antibacterial agent.

[0042] (2) Add 100 g of polyether polyol (model DL-1000) into a container, heat to 120°C and vacuum dehydrate for 2 h, cool to 80°C, add 25 g of diphenylmethane-4,4'-diisocyanate and 0.16 g of dibutyltin dilaurate, and react under nitrogen atmosphere for 2.5 h to obtain component A; cool to room temperature, then add 88 g of polyether polyol (model DL-1000), 4.7 g of chain extender 1,4-butanediol, 5 g of fluorine-containing quaternary ammonium salt antibacterial agent, 16 g of dioctyl adipate, 1.2 g of defoaming agent and 0.12 g of dibutyltin dilaurate as component B, stir and mix to obtain an antibacterial and waterproof adhesive.

[0043] The antibacterial waterproof adhesive was applied to the surfaces of two polyvinyl chloride samples, and the bonding surfaces were bonded to each other, cured at 70°C for 6 hours, and then placed at room temperature for 24 hours. The peel strength was tested according to the method of GB / T 2791-1995. Each sample was tested 3 times and the average value was taken.

[0044] The antibacterial and waterproof adhesive was cured at 70°C for 6 hours to prepare a film sample. The hardness was tested according to the method of GB / T 531.1-2008.

[0045] The film sample was made into a 10cm×10cm×1cm sample, dried, and weighed; completely immersed in water for 48 hours at a water temperature of 25°C. After immersion, the sample was taken out, the surface moisture was wiped off, and the sample was weighed to calculate the water absorption rate W. W=(m-m0) / m0×100%. m0 is the mass of the sample before immersion. m is the mass after immersion.

[0046] Pipette 0.2 mL of 10 5 The bacterial suspension of the test strain with cfu / mL was coated on the surface of the film sample, and then covered with a sterilized polyethylene film, incubated at 37°C in a constant temperature and humidity incubator for 24 hours, and 0.8% sodium chloride solution was used as the eluent to elute the film sample and the polyethylene film surface, and then 0.5mL of the eluent was inoculated on the surface of the nutrient agar medium, incubated at 37°C for 48 hours, and then the viable bacteria were counted. Calculate the antibacterial rate R. R=(BC) / C×100%.

[0047] B is the average number of recovered bacteria in the blank control sample (cfu / piece). The film sample of the antibacterial waterproof adhesive of Comparative Example 1 was used as the blank control sample.

[0048] C is the average number of recovered bacteria in the antimicrobial samples (cfu / tablet).

[0049] The test bacteria were Candida albicans, Escherichia coli and Staphylococcus aureus.

[0050] Table 1 Antibacterial waterproof adhesive performance test

[0051]

[0052] Table 2 Antibacterial rate test of antibacterial waterproof adhesive

[0053]

[0054] After testing, the polyurethane adhesive of each embodiment is added with fluorine-containing quaternary ammonium salt antibacterial agent. Since the molecular main chain of the antibacterial agent contains the same carbamate group as the polyurethane, the fluorine-containing quaternary ammonium salt antibacterial agent and the polyurethane have good interfacial compatibility, and there is almost no adverse effect on the mechanical properties such as the peel strength and the Shore A hardness of the adhesive, which is not much different from the peel strength and the Shore A hardness of the adhesive of Comparative Example 1. And the fluorine-containing quaternary ammonium salt antibacterial agent contains a strong hydrophobic hexafluoroisopropylidene biphenyl structure, which significantly reduces the water absorption rate of the adhesive film, thereby improving the water resistance and waterproof performance of the adhesive. And the fluorine-containing quaternary ammonium salt antibacterial agent has good compatibility with the polyurethane adhesive, is evenly dispersed in the film matrix, and gives the adhesive excellent antibacterial performance, and all shows a high antibacterial rate to Candida albicans, Escherichia coli, and Staphylococcus aureus.

[0055] In Comparative Example 2, 1,10-dichlorodecane and bis(dimethylamino) monomers are used for polymerization reaction. The obtained quaternary ammonium antibacterial agent does not contain the strongly hydrophobic hexafluoroisopropylidene biphenyl structure. The excellent quaternary ammonium antibacterial agent contains a hydrophilic quaternary ammonium group. When added to the polyurethane adhesive, the hydrophilicity of the cured film becomes better, the water absorption rate is increased, and the water resistance and waterproofing performance are poor.

[0056] Comparative Example 3 uses 4,4'-(hexafluoroisopropyl)biphenyl chlorobutyrate and tetramethyl-1,4-butanediamine for polymerization reaction. The obtained fluorine-containing quaternary ammonium salt antibacterial agent does not contain carbamate groups and has poor compatibility with polyurethane. When added to the adhesive, it has a great influence on its mechanical properties, and the peel strength and Shore A hardness decrease significantly.

[0057] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing an antibacterial waterproof adhesive, characterized in that: The preparation method of the antibacterial waterproof adhesive comprises the following steps: S1. Add isopropanol, 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate, and bis(dimethylamino)monomer in a mass ratio of 1:(0.65-0.72) to a flask equipped with a condenser reflux tube, heat to 80-85°C, stir to react for 18-36h, concentrate under reduced pressure, wash with dichloromethane, and dry to obtain a fluorine-containing quaternary ammonium salt antibacterial agent; The structural formula of the 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate is as follows: ； The structural formula of the bis(dimethylamino) monomer is as follows: ； S2. Add 100 parts by weight of polyether polyol to a container, heat and vacuum dehydrate, cool to 70-80° C., add 19-25 parts by weight of diisocyanate and 0.15-0.18 parts by weight of dibutyltin dilaurate, and react under stirring for 2.5-3 hours in a nitrogen atmosphere to obtain component A; cool to room temperature, then add component B, stir and mix to obtain an antibacterial and waterproof adhesive; The component B is composed of 75-88 parts by weight of polyether polyol, 3-6 parts by weight of chain extender, 5-30 parts by weight of fluorine-containing quaternary ammonium salt antibacterial agent, 12-20 parts by weight of dioctyl adipate, 0.8-1.2 parts by weight of defoamer and 0.12-0.16 parts by weight of dibutyltin dilaurate.

2. The method for preparing the antibacterial waterproof adhesive according to claim 1, characterized in that: The diisocyanate is diphenylmethane-4,4'-diisocyanate or toluene-2,4-diisocyanate.

3. The method for preparing the antibacterial waterproof adhesive according to claim 1, characterized in that: The chain extender is 1,4-butanediol, 1,6-hexanediol or trimethylolpropane.

4. The method for preparing the antibacterial waterproof adhesive according to claim 1, characterized in that: The preparation method of the 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate is as follows: placing a flask in an ice bath, adding dichloromethane, hexafluorobisphenol A, triethylamine, and 4-chlorobutyryl chloride, stirring to react, distilling under reduced pressure, washing with water, and drying, dissolving the product in dichloromethane, and recrystallizing to obtain 4,4'-(hexafluoroisopropylidene)biphenyl chlorobutyrate.

5. The method for preparing the antibacterial waterproof adhesive according to claim 4, characterized in that: The mass ratio of hexafluorobisphenol A, triethylamine and 4-chlorobutyryl chloride is 1:(0.6-0.78):(0.84-1.08).

6. The method for preparing the antibacterial waterproof adhesive according to claim 4, characterized in that: The reaction temperature is 20-35°C and the reaction time is 6-10h.

7. The method for preparing the antibacterial waterproof adhesive according to claim 1, characterized in that: The preparation method of the dimethylamino monomer is as follows: toluene, hexamethylene diisocyanate and 3-dimethylamino-1-propanol are added into a flask, stirred to react, low-boiling substances are removed by reduced pressure distillation, petroleum ether is washed, and dried to obtain the dimethylamino monomer.

8. The method for preparing the antibacterial waterproof adhesive according to claim 7, characterized in that: The mass ratio of hexamethylene diisocyanate to 3-dimethylamino-1-propanol is 1:(1.22-1.46).

9. The method for preparing the antibacterial waterproof adhesive according to claim 7, characterized in that: The reaction temperature is 70-85°C and the reaction time is 5-8h.

10. Use of the antibacterial and waterproof adhesive obtained by the preparation method according to any one of claims 1 to 9 in shoe materials.

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