Bacteriostatic environment-friendly two-component polyurethane emulsion

Abstract

The present application relates to the technical fields of polyurethane adhesive, and discloses an antibacterial environment-friendly two-component polyurethane emulsion, which comprises the following raw materials in parts by weight: 50-200 parts of component A; and 2-10 parts of component B; the component A is modified L-lysine organic silicon polyurethane emulsion; and the component B is a mixture of polyester polyol and small molecule alcohol; the antibacterial environment-friendly two-component polyurethane emulsion can be directly used as an adhesive, has mild reaction, and has no color difference, discoloration or glue penetration after gluing.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane adhesive, in particular to a bacteriostatic environment-friendly two-component polyurethane emulsion. BACKGROUND

[0002] Compared with traditional polyurethane products, water-based polyurethane greatly reduces the use of organic solvents, reducing the harm of these substances to the human body. As the current hot water-based product, it has excellent chemical corrosion resistance, good processing performance, and can be widely used in textiles, clothing, construction, home decoration, automobiles and other fields. But it is often disturbed by bacteria and other microorganisms in actual use. Bacteria, fungi and other microorganisms infect and cause serious harm to various fields and threaten human health. This also limits the further promotion of water-based polyurethane materials. Therefore, in order to improve the application value of water-based polyurethane and expand its application range, it is necessary to develop water-based polyurethane materials with antibacterial properties to prepare antibacterial products with excellent performance.

[0003] Polycarbonate polyols (PCDL) can be used to produce polyurethane, acrylic resin, polyester and other products. As one of the latest polyol materials, PCDL has shown strong advantages. The new generation of polycarbonate polyurethane synthesized with PCDL has outstanding performance advantages compared with traditional polyurethane materials: excellent hydrolysis resistance, heat resistance, oxidation resistance, wear resistance, and excellent mechanical properties and microbial degradation, which can be widely used in textiles, medical and other fields.

[0004] Water-based polyurethane is often disturbed by bacteria and other microorganisms in actual use, which limits the further promotion of water-based polyurethane materials. In the existing water-based polyurethane system, the bacteriostatic effect is achieved by adding bactericides. The current CMIT / MIT is a broad-spectrum bactericide developed by SKCN Chemicals based on isothiazolinone technology, but the preservative capacity of MIT / CMIT bactericide is strong, and the content is too high, which can cause irreversible harm to the human body, environment, etc. In recent years, various enterprises including China have strictly investigated products containing CMIT / MIT components, and strictly limited the CMIT / MIT content in imported raw materials or products. By grafting L-lysine on the segment of polyurethane, the structure of polyurethane is improved, so as to change the performance of polyurethane and achieve the purpose of sterilization.

[0005] Secondly, although the traditional waterborne polyurethane emulsion has excellent processability, its water whitening resistance, heat resistance and other properties are still important factors limiting its application expansion. The introduction of polycarbonate polyol introduces repeating carbonate groups into the molecular backbone, greatly improving the hydrolysis resistance of waterborne polyurethane. At the same time, the presence of carbonate groups also makes the group more easily adhere to the substrate surface without changing the structure of the molecule, which improves the high temperature resistance of the adhesive and improves the bonding strength, and there is no color difference before gluing. Therefore, it is of great significance to develop an antibacterial and environmentally friendly polyurethane adhesive. SUMMARY

[0006] The purpose of the present application is to provide an antibacterial and environmentally friendly two-component polyurethane emulsion.

[0007] Term explanation:

[0008] An antibacterial and environmentally friendly two-component polyurethane emulsion comprises the following raw materials by weight:

[0009] A component 50-200 parts;

[0010] B component 2-10 parts;

[0011] The A component is a modified L-lysine polyurethane emulsion; the B component is a mixture of polyester polyol and small molecule alcohol.

[0012] As a preferred technical solution, the mass ratio of the A component to the B component is 100:2-10.

[0013] A method for preparing an antibacterial and environmentally friendly two-component polyurethane emulsion comprises the following steps:

[0014] 1) Preparation of A component: 2500-3000 parts by weight of polycarbonate polyol is added to a reaction kettle, heated to 120-140°C under the protection of nitrogen, vacuum dehydrated for 0.5-1.5h; cooled to 50-60°C, 40-80 parts by weight of No. 1 small molecule alcohol, 0.01-0.1 parts by weight of No. 1 catalyst, 80-120 parts by weight of No. 1 solvent, 600-1000 parts by weight of L-lysine diisocyanate are added, the reaction kettle is heated to 60°C, and the reaction is carried out for 5h. Sample test NCO, after passing, cool to 50°C, add 40-80 parts by weight of chain extender, 5-15 parts by weight of hydrophilic chain extender, continue to react for 2h, sample test reaction endpoint, after cooling, add 20-80 parts by weight of salt forming agent, add 1600-2000 parts by weight of water, 20-60 parts by weight of light stabilizer, 5-8 parts by weight of end-capping agent under high speed dispersion to obtain modified L-lysine polyurethane emulsion, which is component A;

[0015] 2) B component preparation, 20-60 parts by weight of polyester polyol, 3-8 parts by weight of No. 1 small molecule alcohol are added to the emulsification kettle, mixed uniformly, vacuumed to remove moisture, the temperature of the emulsification kettle reaches 130 DEG C, the vacuum time is 1h;

[0016] The reaction kettle polymerization process, 30-70 parts by weight of MDI-50, and 3-6 parts by weight of solvent are added to the reaction kettle, 0.01-0.03 parts by weight of No. 1 catalyst is weighed and added, preheated to 60 DEG C by steam, the components in the emulsification kettle are added to the reaction kettle by valve opening, the dropping speed is controlled, the dropping time is 6h; after dropping, the temperature of the reaction kettle is kept at 70-85 DEG C for 2-5h, the NCO content of the prepolymer is tested, and the temperature is lowered when the temperature of the reaction kettle is lowered to 40-45 DEG C, and the discharge is obtained.

[0017] 3) Use, component A and component B are used together to obtain an antibacterial type environment-friendly two-component polyurethane emulsion; the mass ratio of component A to component B is 100:2-10.

[0018] As a preferred technical scheme, 2700 parts by weight of polycarbonate polyol are added to the reaction kettle in the 1) step; 60 parts by weight of No. 1 small molecule alcohol, 0.05 parts by weight of No. 1 catalyst, 100 parts by weight of No. 1 solvent, 800 parts by weight of L-lysine diisocyanate, 60 parts by weight of chain extender, 10 parts by weight of hydrophilic chain extender, 50 parts by weight of salt forming agent, 1800 parts by weight of water, 40 parts by weight of light stabilizer and 6 parts by weight of blocking agent are added to obtain modified L-lysine polyurethane emulsion under high-speed dispersion state.

[0019] As a preferred technical scheme, 40 parts by weight of polyester polyol and 5 parts by weight of No. 1 small molecule alcohol are added to the emulsification kettle in the 2) step; the reaction kettle polymerization process: 50 parts by weight of MDI-50, and 5 parts by weight of solvent are added to the reaction kettle, and 0.02 parts by weight of No. 1 catalyst is weighed and added.

[0020] As a preferred technical scheme, the small molecule alcohol is 1,4-butanediol; the No. 1 catalyst is an organic bismuth catalyst.

[0021] As a preferred technical scheme, the No. 1 solvent in the 1) is acetone, the chain extender is TMP, the hydrophilic chain extender is DMPA, the salt forming agent is triethylamine, the light stabilizer is Tinuvin292, and the blocking agent is ethylenediamine.

[0022] As a preferred technical solution, the preparation method of polyester polyol in step 2) is as follows: 2500-3000 parts by weight of No. 2 small molecule alcohol is added to the reactor under vacuum, followed by 180-220 parts by weight of TMP, 2800-3200 parts by weight of adipic acid, and 0.1-0.3 parts by weight of antioxidant; the reactor is heated to 250°C and kept at that temperature for 5 hours; after the holding period, 0.01 parts by weight of No. 2 catalyst is added, and the temperature is kept at that temperature for another 5 hours; after the holding period, a vacuum is applied, and after 10 hours of vacuuming, the acid value and hydroxyl value are measured. If the values ​​are qualified, cooling water is circulated to cool the temperature down to 100°C, and the material is discharged to obtain polyester polyol.

[0023] As a preferred technical solution, in step 2), the preparation method of polyester polyol involves adding 2700 parts by weight of No. 2 small molecule alcohol to the reactor under vacuum, followed by adding 200 parts by weight of TMP, 3000 parts by weight of adipic acid, and 0.2 parts by weight of antioxidant. The reactor is then heated to 250°C and held for 5 hours. After the holding period, 0.01 parts by weight of No. 2 catalyst is added, and the reactor is held for another 5 hours. After the holding period, a vacuum is applied, and after 10 hours of vacuuming, the acid value and hydroxyl value are measured. If the values ​​are qualified, cooling water is introduced to lower the temperature to 100°C, and the material is discharged to obtain polyester polyol.

[0024] As a preferred technical solution, the second small molecule alcohol is methylpropanediol, and the second catalyst is tetraisobutyl titanate.

[0025] As a preferred technical solution, after the addition is completed in step 2), the temperature of the reactor is maintained at 80°C for 2 to 5 hours. The NCO content of the prepolymer is tested and tested. After passing the test, the temperature is lowered. When the temperature of the reactor drops to 42°C, the material is discharged.

[0026] The product uses an antibacterial, environmentally friendly two-component polyurethane emulsion, comprising the following raw materials in parts by weight: Component A 50-200 parts; Component B 2-10 parts; Component A is a modified L-lysine polyurethane emulsion; Component B is a mixture of polyester polyol and small molecule alcohol.

[0027] Advantages of this invention:

[0028] The antibacterial and environmentally friendly two-component polyurethane emulsion of the present invention can be used directly as an adhesive. It has a mild reaction and no color difference after application, and no discoloration or glue seepage.

[0029] This invention solves the problem of easy bacterial growth in current waterborne polyurethane emulsion products, effectively reducing bacterial growth and extending product shelf life. Furthermore, the raw materials do not contain bactericides such as MIT / CMIT, ensuring material safety and making it convenient for industry professionals to use.

[0030] By introducing polycarbonate polyols, the hydrolysis resistance of adhesives is effectively improved, resulting in good weather resistance and enhanced water whitening resistance.

[0031] Suitable for bonding nylon hook and loop fasteners. For nylon material, at a speed of 250mm / min, its tensile strength can reach more than 8kN / m and its tensile force can reach more than 140N. Detailed Implementation

[0032] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments.

[0033] Example 1

[0034] 1) Preparation of Component A: 2500 parts by weight of polycarbonate polyol were added to a reaction vessel, heated to 120°C under nitrogen protection, and dehydrated under vacuum for 0.5 h; then cooled to 50°C, 40 parts by weight of No. 1 small molecule alcohol, 0.01 parts by weight of No. 1 catalyst, 80 parts by weight of No. 1 solvent, and 600 parts by weight of L-lysine diisocyanate were added. The reaction vessel was heated to 60°C and reacted for 5 h. NCO was tested and found to be qualified. The temperature was then lowered to 50°C, 40 parts by weight of chain extender and 5 parts by weight of hydrophilic chain extender were added, and the reaction was continued for 2 h. The reaction endpoint was tested and found. After cooling, 20 parts by weight of salt-forming agent were added. Under high-speed dispersion, 1600 parts by weight of water, 20 parts by weight of light stabilizer, and 5 parts by weight of end-capping agent were added to obtain the modified L-lysine polyurethane emulsion, i.e., component A.

[0035] 2) Preparation of component B: Add 20 parts by weight of polyester polyol and 3 parts by weight of No. 1 small molecule alcohol to the emulsification kettle, mix evenly, remove moisture by vacuum, start timing when the temperature of the emulsification kettle reaches 130℃, and the vacuuming time is 1 hour.

[0036] In the reactor polymerization process, 30 parts by weight of MDI-50 and 3 parts by weight of solvent were added to the reactor, along with 0.01 parts by weight of catalyst No. 1. The reactor was preheated to 60°C with steam. The components in the emulsion vessel were then added dropwise to the reactor by adjusting the valve opening, controlling the dropping rate, and the dropping time was 6 hours. After the dropping was completed, the reactor temperature was maintained at 70°C for 2 hours. The NCO content of the prepolymer was tested, and after passing the test, the temperature was lowered. When the reactor temperature dropped to 40°C, the material was discharged to obtain component B.

[0037] 3) When using, use component A and component B together to obtain an antibacterial and environmentally friendly two-component polyurethane emulsion; the mass ratio of component A to component B is 100:2.

[0038] The small molecule alcohol is 1.4-butanediol; the first catalyst is an organic bismuth catalyst.

[0039] The first solvent in the 1) is acetone, the chain extender is TMP, the hydrophilic chain extender is DMPA, the salt forming agent is triethylamine, the light stabilizer is Tinuvin 292, and the end capping agent is ethylenediamine.

[0040] The preparation method of the polyester polyol in the 2) is:

[0041] The vacuum method is used to add 2500 parts by weight of the second small molecule alcohol into the reaction kettle, then add 180 parts by weight of TMP, 2800 parts by weight of adipic acid, and 0.1 parts by weight of antioxidant;

[0042] The reaction kettle is heated to 250℃, and kept for 5h; after the heat preservation is completed, 0.01 parts by weight of the second catalyst is added, and then kept for 5h; after the heat preservation is completed, vacuumizing is carried out, and the acid value and hydroxyl value are measured after vacuumizing for 10h; after passing, cooling water is used to cool down to 100℃, and the product is discharged to obtain the polyester polyol.

[0043] The second small molecule alcohol is methylpropylene glycol, and the second catalyst is titanium tetraisobutylate.

[0044] Example 2

[0045] 1) A component preparation, 3000 parts by weight of polycarbonate polyol is added into the reaction kettle, heated to 140℃ under the protection of nitrogen, and vacuumized for 1.5h; cooled to 60℃, 80 parts by weight of the first small molecule alcohol, 0.1 parts by weight of the first catalyst, 120 parts by weight of the first solvent, 1000 parts by weight of L-lysine diisocyanate are added, the reaction kettle is heated to 60℃, and reacted for 5h; after sampling and testing NCO, it is qualified, cooled to 50℃, 80 parts by weight of chain extender, 15 parts by weight of hydrophilic chain extender are added, and continue to react for 2h; after cooling, 80 parts by weight of salt forming agent is added, 2000 parts by weight of water, 60 parts by weight of light stabilizer, and 8 parts by weight of end capping agent are added in high speed dispersion state to obtain modified L-lysine polyurethane emulsion, which is component A;

[0046] 2) B component preparation, 60 parts by weight of polyester polyol, 8 parts by weight of the first small molecule alcohol are added into the emulsifying kettle, mixed uniformly, vacuumized to remove moisture, the emulsifying kettle temperature reaches 130℃, and the vacuumizing time is 1h;

[0047] The reaction kettle polymerization process, 70 parts by weight of MDI-50, and 6 parts by weight of solvent are added to the reaction kettle, 0.03 parts by weight of No. 1 catalyst is weighed and added, preheated to 60℃ by steam, and the components in the emulsification kettle are added to the reaction kettle by valve opening, and the dropping speed is controlled, and the dropping time is 6h; after the dropping is completed, the temperature of the reaction kettle is kept at 85℃ for 5h, the NCO content of the prepolymer is tested, and after the qualified, the temperature is lowered, and when the temperature of the reaction kettle is lowered to 45℃, the discharge is obtained, and component B is obtained;

[0048] 3) Use, component A and component B are used together to obtain an antibacterial type environment-friendly two-component polyurethane emulsion; the mass ratio of component A to component B is 100:10.

[0049] The small molecule alcohol is 1.4-butanediol; the No. 1 catalyst is an organic bismuth catalyst.

[0050] The No. 1 solvent in 1) is acetone, the chain extender is TMP, the hydrophilic chain extender is DMPA, the salt forming agent is triethylamine, the light stabilizer is Tinuvin292, and the end capping agent is ethylenediamine.

[0051] The preparation method of the polyester polyol in the step 2) is:

[0052] The No. 2 small molecule alcohol is methylpropylene glycol, and the No. 2 catalyst is titanium isobutylate.

[0053] The reaction kettle is heated to 250℃, and kept for 5h; after the heat preservation is finished, 0.01 parts by weight of No. 2 catalyst is added, and then kept for 5h; after the heat preservation is finished, vacuumizing is carried out, and the acid value and the hydroxyl value are measured after vacuumizing for 10h; after the qualified, cooling water is passed to lower the temperature, and the temperature is lowered to 100℃; the discharge is obtained, and the polyester polyol is obtained.

[0054] The No. 2 small molecule alcohol is methylpropylene glycol, and the No. 2 catalyst is titanium isobutylate. Example

[0055] 1) Preparation of component A, 2700 parts by weight of polycarbonate polyol is added to the reaction kettle, heated to 130℃ under the protection of nitrogen, vacuum dehydration for 1h; cooling to 55℃, adding 60 parts by weight of No. 1 small molecule alcohol, 0.05 parts by weight of No. 1 catalyst, adding 100 parts by weight of No. 1 solvent, adding 800 parts by weight of L-lysine diisocyanate, the reaction kettle is heated to 60℃, and the reaction is carried out for 5h, sampling test NCO, qualified, cooling to 50℃, adding 60 parts by weight of chain extender, 10 parts by weight of hydrophilic chain extender, continuing to react for 2h, sampling test reaction endpoint, after cooling, adding 50 parts by weight of salt forming agent, adding 1800 parts by weight of water, 2400 parts by weight of light stabilizer, 6 parts by weight of capping agent under high speed dispersion to obtain modified L-lysine polyurethane emulsion, namely component A;

[0056] 2) Preparation of component B, 40 parts by weight of polyester polyol, 6 parts by weight of No. 1 small molecule alcohol is added to the emulsification kettle, mixed uniformly, vacuum dehydration, the temperature of the emulsification kettle reaches 130℃, and the vacuum time is 1h;

[0057] Polymerization process of the reaction kettle, 50 parts by weight of MDI-50, and 5 parts by weight of solvent are added to the reaction kettle, 0.02 parts by weight of No. 1 catalyst is weighed and added, preheated to 60℃ by steam, the emulsification kettle is added to the reaction kettle by valve opening, the dropping speed is controlled, and the dropping time is 6h; After dropping, the temperature of the reaction kettle is kept at 80℃ for 3.5h, the NCO content of the prepolymer is tested, qualified, and when the temperature of the reaction kettle drops to 42℃, the discharge is obtained, and component B is obtained;

[0058] 3) In use, component A is used with component B to obtain an antibacterial type environment-friendly two-component polyurethane emulsion; the mass ratio of component A to component B is 100:2-10.

[0059] The small molecule alcohol is 1.4-butylene glycol; the No. 1 catalyst is an organic bismuth catalyst.

[0060] The No. 1 solvent in 1) is acetone, the chain extender is TMP, the hydrophilic chain extender is DMPA, the salt forming agent is triethylamine, the light stabilizer is Tinuvin292, and the capping agent is ethylenediamine.

[0061] The preparation method of the polyester polyol in the step 2) is:

[0062] The reaction kettle is added with 2700 parts by weight of No. 2 small molecule alcohol, then 200 parts by weight of TMP, 3000 parts by weight of adipic acid, and 0.2 parts by weight of antioxidant are added;

[0063] The reactor is heated to 250 DEG C, and kept for 5 hours; after the keeping, 0.01 parts by weight of the second catalyst is added, and kept for 5 hours; after the keeping, vacuum is drawn, and the acid value and the hydroxyl value are measured after 10 hours of vacuum drawing; after the values are qualified, cooling water is passed to cool down to 100 DEG C, and the product is discharged, to obtain the polyester polyol.

[0064] The second small molecule alcohol is methyl propylene glycol, and the second catalyst is tetraisobutyl titanate.

[0065] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application, and various changes and improvements can be made without departing from the spirit and scope of the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an antibacterial, environmentally friendly two-component polyurethane emulsion, characterized in that, Includes the following steps: 1) Preparation of Component A: 2500–3000 parts by weight of polycarbonate polyol are added to a reaction vessel. Under nitrogen protection, the temperature is raised to 120–140°C, and dehydrated under vacuum for 0.5–1.5 hours. The temperature is then lowered to 50–60°C, and 40–80 parts by weight of 1,4-butanediol, 0.01–0.1 parts by weight of catalyst No. 1, 80–120 parts by weight of solvent No. 1, and 600–1000 parts by weight of L-lysine diisocyanate are added. The reaction... The reactor is heated to 60℃ and reacted for 5 hours. A sample is taken to test the NCO content. After passing the test, the temperature is lowered to 50℃, and 40-80 parts by weight of chain extender and 5-15 parts by weight of hydrophilic chain extender are added. The reaction continues for 2 hours, and a sample is taken to test the reaction endpoint. After cooling, 20-80 parts by weight of salt-forming agent are added. Under high-speed dispersion, 1600-2000 parts by weight of water, 20-60 parts by weight of light stabilizer, and 5-8 parts by weight of end-capping agent are added to obtain the modified L-lysine polyurethane emulsion, i.e., component A. 2) Preparation of component B: Add 20-60 parts by weight of polyester polyol and 3-8 parts by weight of 1,4-butanediol to the emulsification kettle, mix evenly, remove moisture by vacuum, start timing when the temperature of the emulsification kettle reaches 130℃, and the vacuuming time is 1 hour. In the reactor polymerization process, 30-70 parts by weight of MDI-50 and 3-6 parts by weight of solvent are added to the reactor. 0.01-0.03 parts by weight of catalyst No. 1 are also added. The reactor is preheated to 60°C with steam. The components in the emulsion reactor are added dropwise to the reactor by adjusting the valve opening, controlling the dropping rate, and the dropping time is 6 hours. After the dropping is complete, the reactor temperature is maintained at 70-85°C for 2-5 hours. The NCO content of the prepolymer is tested. If it is qualified, the temperature is lowered. When the reactor temperature drops to 40-45°C, the material is discharged to obtain component B. 3) When using, use component A and component B together to obtain an antibacterial and environmentally friendly two-component polyurethane emulsion; the mass ratio of component A to component B is 100:2 to 10.

2. The method for preparing an antibacterial, environmentally friendly two-component polyurethane emulsion as described in claim 1, characterized in that: The catalyst No. 1 is an organic bismuth catalyst.

3. The method for preparing an antibacterial, environmentally friendly two-component polyurethane emulsion as described in claim 1, characterized in that: In step 1), solvent 1 is acetone, chain extender is TMP, hydrophilic chain extender is DMPA, salt forming agent is triethylamine, light stabilizer is Tinuvin 292, and end-capping agent is ethylenediamine.

4. The method for preparing an antibacterial, environmentally friendly two-component polyurethane emulsion as described in claim 1, characterized in that, The preparation method of polyester polyol in step 2) is as follows: 2500-3000 parts by weight of No. 2 small molecule alcohol is added to the reaction vessel under vacuum, followed by 180-220 parts by weight of TMP, 2800-3200 parts by weight of adipic acid, and 0.1-0.3 parts by weight of antioxidant; the reaction vessel is heated to 250°C and kept at that temperature for 5 hours. After the heat preservation is completed, 0.01 parts by weight of catalyst No. 2 is added, and the heat preservation is continued for another 5 hours. After the heat preservation is completed, vacuuming is performed. After vacuuming for 10 hours, the acid value and hydroxyl value are measured. If they are qualified, cooling water is circulated to cool down to 100°C. The material is then discharged to obtain polyester polyol.

5. The method for preparing an antibacterial, environmentally friendly two-component polyurethane emulsion as described in claim 4, characterized in that: The second small molecule alcohol is methylpropanediol, and the second catalyst is tetraisobutyl titanate.

6. The method for preparing an antibacterial, environmentally friendly two-component polyurethane emulsion as described in claim 3, characterized in that: After the addition in step 2) is completed, maintain the temperature of the reactor at 80°C for 2-5 hours, take a sample to test the NCO content of the prepolymer, and cool it down after it passes the test. When the temperature of the reactor drops to 42°C, discharge the material.

7. An antibacterial and environmentally friendly two-component polyurethane emulsion prepared by the method for preparing an antibacterial and environmentally friendly two-component polyurethane emulsion as described in any one of claims 1 to 6.