Bio-based polyurea sealant and preparation method thereof

Abstract

The invention relates to the technical field of sealant preparation, in particular to a bio-based polyurea sealant and a preparation method thereof.The bio-based polyurea sealant is prepared from 3-8 parts of modified amino silicon oil prepolymer, 15-20 parts of polyether polyol prepolymer, 50-60 parts of polyaspartic acid ester, 15-20 parts of hydrophobic glass beads, 45-50 parts of deionized water and 3-5 parts of antibacterial agent. 2-benzisothiazole-3-ketone is used as an antifouling active substance and is grafted into aminopropyl polydimethylsiloxane after being modified, 3, 4-diaminofurazan is used as a chain extender, ZnCl2 is added to form a modified amino silicon oil prepolymer, hydrogen bonds are formed among urea bonds in a polymer system, metal coordination bonds are formed by 3, 4-diaminofurazan and Zn < 2 + >, and the modified amino silicon oil prepolymer is formed by adding ZnCl2. The interaction between molecular chains is enhanced, so that the bio-based polyurea sealant has excellent antifouling property and good mechanical property, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of seam beautifying agent preparation, and in particular to a bio-based polyurea seam beautifying agent and a preparation method thereof. Background Art

[0002] Traditional caulking agents made from bio-based materials are usually made from renewable resources, such as vegetable oil, soybean oil, etc., which reduces dependence on non-renewable resources. At the same time, due to the use of natural raw materials, bio-based caulking agents release fewer harmful substances during the production process and have less impact on human health. However, traditional caulking agents made from bio-based materials are slightly lacking in durability. Due to the chemical properties of the bio-based materials themselves, the caulking agents made from them may change color, decrease in hardness, or slightly wear after long-term use. At the same time, their anti-fouling properties are poor, especially for oily stains and difficult-to-remove dirt, which may be more difficult to clean and maintain.

[0003] For example, in the prior art, bio-based polyurea seam beautifier is generally prepared by using polyaspartic acid ester. However, due to the shortcomings of the polyaspartic acid ester itself, the temperature resistance, flexibility and antifouling properties of the finally prepared seam beautifier cannot meet the application requirements in some special occasions or application fields, so the material needs to be modified.

[0004] Therefore, according to the above-mentioned related technologies, it is urgent to develop a bio-based polyurea seam beautifying agent and a preparation method thereof. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a bio-based polyurea seam beautifying agent and a preparation method thereof, so as to provide a preparation method that takes into account both antifouling properties and mechanical properties.

[0006] Based on the above purpose, the present invention provides a bio-based polyurea seam beautifying agent and a preparation method thereof.

[0007] A bio-based polyurea seam beautifying agent is prepared from the following raw materials by weight: 3-8 parts of modified amino silicone oil prepolymer, 15-20 parts of polyether polyol prepolymer, 50-60 parts of polyaspartic acid ester, 15-20 parts of hydrophobic glass microbeads, 45-50 parts of deionized water, and 3-5 parts of antibacterial agent;

[0008] The modified amino silicone oil prepolymer is prepared from 1,2-benzisothiazol-3-one, isophorone diisocyanate, amino silicone oil, 3,4-diaminofurazole and ZnCl2.

[0009] Preferably, the amino silicone oil is aminopropyl polydimethylsiloxane.

[0010] Preferably, the particle size of the hydrophobic glass microbeads is 150-300 mesh.

[0011] Preferably, the antibacterial agent is any one of nano zinc oxide and nano silver.

[0012] Preferably, the preparation method of the modified amino silicone oil prepolymer is as follows:

[0013] Step A1. At room temperature, add isophorone diisocyanate solution dropwise to 1,2-benzisothiazol-3-one solution, and react at 60-70°C for 3-5h to obtain a mixed solution A;

[0014] Step A2. Add the mixed solution A dropwise into the aminopropyl polydimethylsiloxane solution and react at room temperature for 3-5 hours to obtain a prepolymer B;

[0015] Step A3. Add 3,4-diaminofurazole to prepolymer B, react at 50-70°C for 3-5 hours, add ZnCl2, and stir for 1-2 hours to obtain a modified amino silicone oil prepolymer.

[0016] Preferably, the isophorone diisocyanate solution in step A1 is obtained by dissolving 7-10 g of isophorone diisocyanate in 60-80 mL of tetrahydrofuran;

[0017] The 1,2-benzisothiazol-3-one solution in step A1 is obtained by dissolving 5-8 g of 1,2-benzisothiazol-3-one in 40-50 mL of tetrahydrofuran;

[0018] The volume ratio of the isophorone diisocyanate solution and the 1,2-benzisothiazol-3-one solution in step A1 is 60-80:40-50;

[0019] The aminopropyl polydimethylsiloxane solution in step A2 is 40-45 g of aminopropyl polydimethylsiloxane dissolved in 400-40 mL of tetrahydrofuran.

[0020] Preferably, the mass ratio of 3,4-diaminofurazole, prepolymer B and ZnCl2 in step A3 is 1-1.2:10-12:0.3-0.5.

[0021] Preferably, the preparation method of the polyether polyol prepolymer is as follows:

[0022] Mix polytetrahydrofuran diol, polypropylene glycol and dibutyltin dilaurate, stir at 100-105°C for 30-40 minutes and then cool to room temperature, drop isophorone diisocyanate solution into the mixed solution, and after the dropwise addition is completed, heat the system to 80-85°C and react for 2-3 hours to obtain a polyether polyol prepolymer.

[0023] Preferably, the dosage ratio of the polytetrahydrofuran diol, polypropylene glycol, dibutyltin dilaurate, and isophorone diisocyanate solution is 40-45 g: 60-65 g: 0.1-0.3 g: 450-480 mL;

[0024] The isophorone diisocyanate solution is prepared by dissolving 45-50 g of isophorone diisocyanate in 450-480 mL of tetrahydrofuran.

[0025] Preferably, the preparation method of the polyaspartic acid ester is as follows:

[0026] Step B1. extracting L-aspartic acid by biological fermentation, and performing polymerization dehydration reaction at 200° C. to obtain intermediate Ⅰ;

[0027] Step B2. Dissolve intermediate I in NaOH solution, hydrolyze at room temperature for 1-2 hours, adjust the pH to 7, place it in a water bath, evaporate at 80-85°C for 1-3 hours, filter under reduced pressure, collect the precipitate in a watch glass, and dry it in a thermostat at 105°C for 2 hours to obtain intermediate II;

[0028] Step B3. React intermediate II, methanol and p-toluenesulfonic acid at 30-50°C for 1-3h, filter three times and dry in a constant temperature oven at 105°C for 3h to obtain polyaspartic acid ester.

[0029] Preferably, in step B2, the ratio of the intermediate I to the NaOH solution is 80-90 g: 800-900 mL, and the concentration of the NaOH solution is 3.33 mol / L;

[0030] The usage ratio of intermediate II, methanol and p-toluenesulfonic acid in step B3 is 70-80 g:450-500 mL:8-10 g.

[0031] Preferably, the method for preparing the bio-based polyurea seam beautifying agent comprises the following steps:

[0032] The modified amino silicone oil prepolymer and the polyether polyol prepolymer are mixed in a rotary and revolving mixer at a speed of 2000 r / min for 2-5 minutes, and then polyaspartic acid ester, hydrophobic glass microbeads and antibacterial agent are added. After stirring for 5-7 minutes, degassing is carried out at 2000 r / min for 1-2 minutes. The mixture is placed in a vacuum oven and dried at 50°C for 3-5 hours. Deionized water is added and mixed evenly to obtain a bio-based polyurea seam beautifying agent.

[0033] Beneficial effects of the present invention:

[0034] The present invention selects 1,2-benzisothiazol-3-one as the antifouling active substance, which is modified and then connected to aminopropyl polydimethylsiloxane. 3,4-diaminofurazole is used as a chain extender, and ZnCl2 is added to form a modified amino silicone oil prepolymer, so that the seam beautifying agent has excellent antifouling properties while also having good mechanical properties.

[0035] The modified amino silicone oil prepolymer provided by the present invention has a network structure, and the crosslinking density of the prepared seam beautifying agent increases; aminopropyl polydimethylsiloxane reacts with isocyanate to form urea bonds, and hydrogen bonds are formed between the urea bonds in the polymer system, and 3,4-diaminofurazan and Zn 2+ The formation of metal coordination bonds enhances the interaction between molecular chains. The combined effect of these two aspects gives the seam beautifier excellent mechanical properties. DETAILED DESCRIPTION

[0036] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0037] The sources and properties of some of the raw materials used in the present invention are as follows:

[0038] Aminopropyl polydimethylsiloxane was purchased from Suzhou Qitian New Materials Co., Ltd.; 1,2-benzisothiazol-3-one was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; isophorone diisocyanate was purchased from Yantai Wanhua Chemical Group Co., Ltd.; 3,4-diaminofurazar was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0039] Embodiment 1: A method for preparing a bio-based polyurea seam beautifying agent, comprising the following steps:

[0040] S1. 8g of 1,2-benzisothiazol-3-one was dissolved in 50mL of tetrahydrofuran to prepare a 1,2-benzisothiazol-3-one solution, 10g of isophorone diisocyanate was dissolved in 80mL of tetrahydrofuran to prepare an isophorone diisocyanate solution, the 1,2-benzisothiazol-3-one solution was added to a thermometer and a condensation device, the isophorone diisocyanate solution was slowly added dropwise at room temperature, the condensation water was opened after the addition was completed, the mixture was reacted at 70°C for 5h and then cooled to room temperature to obtain a mixed solution A;

[0041] S2. Weigh 45 g of aminopropyl polydimethylsiloxane and add 420 mL of tetrahydrofuran to dissolve it to prepare an aminopropyl polydimethylsiloxane solution. Slowly add the mixture A dropwise to the aminopropyl polydimethylsiloxane solution and react at room temperature for 5 h to obtain a prepolymer B.

[0042] S3. Add 1.2 g of 3,4-diaminofurazole to 12 g of prepolymer B, react at 70°C for 5 h, add 0.5 g of ZnCl2, and stir for 2 h to obtain a modified amino silicone oil prepolymer.

[0043] S4. Weigh 45g of polytetrahydrofuran diol, 65g of polypropylene glycol, and 0.3g of dibutyltin dilaurate, add them into a three-necked flask with mechanical stirring and a thermometer, stir at 105°C for 40min, and then cool to room temperature. Dissolve 50g of isophorone diisocyanate in tetrahydrofuran and slowly drop the isophorone diisocyanate solution into the three-necked flask. After the dropwise addition is completed, heat the system to 85°C and react for 3h to obtain a polyether polyol prepolymer.

[0044] S5. After mixing 8g of modified amino silicone oil prepolymer and 20g of polyether polyol prepolymer in a rotary mixer at a speed of 2000r / min for 5min, 60g of polyaspartic acid ester, 20g of hydrophobic glass microbeads and 5g of nano zinc oxide were added. After stirring for 7min, degassing was carried out at 2000r / min for 2min. The mixture was placed in a vacuum oven and dried at 50°C for 5h. 50mL of deionized water was added and mixed evenly to obtain a bio-based polyurea seam beautifying agent, wherein the particle size of the hydrophobic glass microbeads is 300 mesh.

[0045] Embodiment 2: A method for preparing a bio-based polyurea seam beautifying agent, comprising the following steps:

[0046] S1. 7g of 1,2-benzisothiazol-3-one was dissolved in 48mL of tetrahydrofuran to prepare a 1,2-benzisothiazol-3-one solution, 9g of isophorone diisocyanate was dissolved in 75mL of tetrahydrofuran to prepare an isophorone diisocyanate solution, the 1,2-benzisothiazol-3-one solution was added to a thermometer and a condensation device, and the isophorone diisocyanate solution was slowly added dropwise at room temperature. After the addition was completed, the condensation water was opened, and the mixture was reacted at 68°C for 4.5h and then cooled to room temperature to obtain a mixed solution A;

[0047] S2. Weigh 44 g of aminopropyl polydimethylsiloxane and add 415 mL of tetrahydrofuran to dissolve it to prepare an aminopropyl polydimethylsiloxane solution. Slowly add the mixture A dropwise to the aminopropyl polydimethylsiloxane solution and react at room temperature for 4.5 h to obtain a prepolymer B.

[0048] S3. Add 1.2 g of 3,4-diaminofurazole to 12 g of prepolymer B, react at 65° C. for 4.5 h, add 0.5 g of ZnCl2, and stir for 2 h to obtain a modified amino silicone oil prepolymer.

[0049] S4. Weigh 45g of polytetrahydrofuran diol, 65g of polypropylene glycol, and 0.3g of dibutyltin dilaurate, add them into a three-necked flask with mechanical stirring and a thermometer, stir at 104°C for 38min, and then cool to room temperature. Dissolve 50g of isophorone diisocyanate in tetrahydrofuran and slowly drop the isophorone diisocyanate solution into the three-necked flask. After the dropwise addition is completed, heat the system to 84°C and react for 3h to obtain a polyether polyol prepolymer.

[0050] S5. After mixing 6 g of modified amino silicone oil prepolymer and 19 g of polyether polyol prepolymer in a rotary mixer at a speed of 2000 r / min for 4 min, 58 g of polyaspartic acid ester, 19 g of hydrophobic glass microbeads and 4 g of nano zinc oxide were added. After stirring for 6 min, degassing was performed at 2000 r / min for 2 min. The mixture was placed in a vacuum oven and dried at 50°C for 4 h. 48 mL of deionized water was added and mixed evenly to obtain a bio-based polyurea seam beautifying agent, wherein the particle size of the hydrophobic glass microbeads is 280 mesh.

[0051] Embodiment 3: A method for preparing a bio-based polyurea seam beautifying agent, comprising the following steps:

[0052] S1. 6 g of 1,2-benzisothiazol-3-one was dissolved in 45 mL of tetrahydrofuran to prepare a 1,2-benzisothiazol-3-one solution, and 8 g of isophorone diisocyanate was dissolved in 70 mL of tetrahydrofuran to prepare an isophorone diisocyanate solution. The 1,2-benzisothiazol-3-one solution was added to a thermometer and a condensation device, and the isophorone diisocyanate solution was slowly added dropwise at room temperature. After the addition was completed, the condensation water was opened, and the mixture was reacted at 63° C. for 4 hours and then cooled to room temperature to obtain a mixed solution A;

[0053] S2. Weigh 42 g of aminopropyl polydimethylsiloxane and add 410 mL of tetrahydrofuran to dissolve it to prepare an aminopropyl polydimethylsiloxane solution. Slowly add the mixture A dropwise to the aminopropyl polydimethylsiloxane solution and react at room temperature for 4 h to obtain a prepolymer B.

[0054] S3. Add 1.2 g of 3,4-diaminofurazole to 12 g of prepolymer B, react at 60°C for 4 h, add 0.5 g of ZnCl2, and stir for 1 h to obtain a modified amino silicone oil prepolymer.

[0055] S4. Weigh 45g of polytetrahydrofuran diol, 65g of polypropylene glycol, and 0.3g of dibutyltin dilaurate, add them into a three-necked flask with mechanical stirring and a thermometer, stir at 102°C for 32min, and then cool to room temperature. Dissolve 50g of isophorone diisocyanate in tetrahydrofuran and slowly drop the isophorone diisocyanate solution into the three-necked flask. After the dropwise addition is completed, heat the system to 82°C and react for 2h to obtain a polyether polyol prepolymer.

[0056] S5. After mixing 5g of modified amino silicone oil prepolymer and 17g of polyether polyol prepolymer in a rotary and revolving mixer at a speed of 2000r / min for 3.5min, 56g of polyaspartic acid ester, 17g of hydrophobic glass microbeads and 3g of nanosilver were added. After stirring for 6min, degassing was carried out at 2000r / min for 1min. The mixture was placed in a vacuum oven and dried at 50°C for 3h. 46mL of deionized water was added and mixed evenly to obtain a bio-based polyurea seam beautifying agent, wherein the particle size of the hydrophobic glass microbeads is 200 mesh.

[0057] Embodiment 4: A method for preparing a bio-based polyurea seam beautifying agent, comprising the following steps:

[0058] S1. 5 g of 1,2-benzisothiazol-3-one was dissolved in 40 mL of tetrahydrofuran to prepare a 1,2-benzisothiazol-3-one solution, and 7 g of isophorone diisocyanate was dissolved in 60 mL of tetrahydrofuran to prepare an isophorone diisocyanate solution. The 1,2-benzisothiazol-3-one solution was added to a thermometer and a condensation device, and the isophorone diisocyanate solution was slowly added dropwise at room temperature. After the addition was completed, the condensation water was opened, and the mixture was reacted at 60° C. for 3 h and then cooled to room temperature to obtain a mixed solution A.

[0059] S2. Weigh 40 g of aminopropyl polydimethylsiloxane and add 400 mL of tetrahydrofuran to dissolve it to prepare an aminopropyl polydimethylsiloxane solution. Slowly add the mixture A dropwise to the aminopropyl polydimethylsiloxane solution and react at room temperature for 3 h to obtain a prepolymer B.

[0060] S3. Add 1.2 g of 3,4-diaminofurazole to 12 g of prepolymer B, react at 50°C for 3 h, add 0.5 g of ZnCl2, and stir for 1 h to obtain a modified amino silicone oil prepolymer.

[0061] S4. Weigh 45g of polytetrahydrofuran diol, 65g of polypropylene glycol, and 0.3g of dibutyltin dilaurate, add them into a three-necked flask with mechanical stirring and a thermometer, stir at 100°C for 30min, and then cool to room temperature. Dissolve 50g of isophorone diisocyanate in tetrahydrofuran and slowly drop the isophorone diisocyanate solution into the three-necked flask. After the dropwise addition is completed, heat the system to 80-85°C and react for 2h to obtain a polyether polyol prepolymer.

[0062] S5. Mix 3g of modified amino silicone oil prepolymer and 15g of polyether polyol prepolymer in a rotary mixer at a speed of 2000r / min for 2min, then add 50g of polyaspartic acid ester, 20g of hydrophobic glass microbeads, and 5g of nanosilver. After stirring for 5min, deaerate at 2000r / min for 1min, put the mixture into a vacuum oven at 50°C for 3h, add 45mL of deionized water and mix well to obtain a bio-based polyurea seam beautifying agent, wherein the particle size of the hydrophobic glass microbeads is 150 mesh.

[0063] Comparative Example 1:

[0064] Compared with Example 1, this comparative example did not add 1,2-benzisothiazol-3-one during the preparation of the modified aminosilicone oil prepolymer, and the remaining steps and parameters were the same, which will not be repeated in this comparative example, and finally a bio-based polyurea seam beautifying agent was obtained.

[0065] Comparative Example 2:

[0066] Compared with Example 1, this comparative example did not add 3,4-diaminofurazole during the preparation of the modified amino silicone oil prepolymer, and the remaining steps and parameters were the same, which will not be repeated in this comparative example, and finally a bio-based polyurea seam beautifying agent was obtained.

[0067] Comparative Example 3:

[0068] Compared with Example 1, ZnCl2 was not added during the preparation of the modified amino silicone oil prepolymer in this comparative example. The remaining steps and parameters were the same, and this comparative example will not be repeated. Finally, a bio-based polyurea seam beautifying agent was obtained.

[0069] Comparative Example 4:

[0070] Compared with Example 1, the modified amino silicone oil prepolymer was not added during the preparation of the bio-based polyurea seam beautifying agent in this comparative example, and the remaining steps and parameters were the same, which will not be repeated in this comparative example, and finally the bio-based polyurea seam beautifying agent was obtained.

[0071] Performance Test:

[0072] The treated steel plates with a size of 120 mm × 60 mm were placed on the test bench, and the bio-based polyurea seam beautifying agents prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were respectively coated on each group of steel plates using a wire rod coater with a specification of 100 μm, and the wet film thickness was 100 μm. After coating the seam beautifying agent, the sample was placed flat on the test bench and dried at 25°C for 24 hours to obtain a coating sample. The prepared coating sample was subjected to performance tests:

[0073] Wettability test:

[0074] With reference to the GB / T30693-2014 test standard, the surface wettability of the bio-based polyurea seam beautifier was studied by static water contact angle test. The bio-based polyurea seam beautifier prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 5 was applied on a sample plate, and 4L of pure water was dripped on the coating surface using a water contact angle meter (OCA-25). After the water droplets were stable, photos were taken and the contact angle was calculated. Five different positions of each coating were randomly selected for measurement, and the final result was averaged.

[0075] Adhesion test:

[0076] According to the GB / T5210-2006 test standard, the bio-based polyurea seam beautifying agent prepared in Example 1-Example 4 and Comparative Example 1-Comparative Example 5 was applied to the sample. The diameter of the aluminum alloy cylinder was 20 mm. The clean aluminum alloy cylinder and the sample were bonded by an adhesive and left to stand for 48 hours. After the adhesive was completely cured, it was pulled using a Positest-AT-M tensile testing machine. During the pulling process, stress was applied in a direction perpendicular to the substrate, and the pulling speed was 0.2 MPa per second. The value when the cylinder fell off the substrate surface was recorded. Five different points were randomly selected for each sample for testing, and the average value was taken as the final result.

[0077] Tensile properties test:

[0078] According to the GBT1040-92 test standard, the bio-based polyurea seam beautifying agent prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 5 was applied to a dumbbell-shaped mold, wherein the effective length was 20 mm, the width was 4 mm, and the thickness was 2 mm. The experimental instrument was a 3365 universal tensile testing machine from Instron, USA. The experimental tensile rate was 100 mm / min, and the experimental temperature was room temperature. After the experiment, the tensile strength, elongation at break and other data of the samples were recorded;

[0079] The tensile strength is calculated according to the following formula:

[0080] Tensile strength calculation formula:

[0081] p is the load on the specimen when it breaks, in Newton (N); b is the width of the specimen, in millimeters (mm); d is the thickness of the specimen, in millimeters (mm).

[0082] Elongation at break calculation formula:

[0083] G is the distance between the marking lines when the specimen breaks, in millimeters (mm); G0 is the original distance of the specimen, in millimeters (mm).

[0084] Anti-pollution performance test:

[0085] Referring to the JC / T463-2014 test standard, the bio-based polyurea seam beautifier prepared in Examples 1 to 4 and Comparative Examples 1 to 5 was applied to the sample, and the antifouling effect was tested with soy sauce and colored vinegar. The same pollutant was applied at two locations on the same sample, and the application area of ​​each location was about 25 cm 2 , carry out cleaning and anti-pollution performance rating according to the prescribed steps, and take the larger value of the pollution resistance grade at two locations on the same sample as the test result for the pollutant.

[0086] Table 1 Summary of experimental data in Examples 1-4 and Comparative Examples 1-5

[0087]

[0088] Data Analysis:

[0089] As can be seen from Table 1, the bio-based polyurea seam beautifying agent prepared by the present invention has better antifouling properties while taking into account mechanical properties. The present invention selects 1,2-benzisothiazol-3-one as the antifouling active substance, and after modification, it is connected to aminopropyl polydimethylsiloxane, and 3,4-diaminofurazole is used as a chain extender. After adding ZnCl2, a modified aminosilicone oil prepolymer is formed, so that the seam beautifying agent has excellent antifouling properties while taking into account good mechanical properties. The modified aminosilicone oil prepolymer is a network structure, and the crosslinking density of the prepared seam beautifying agent increases; aminopropyl polydimethylsiloxane reacts with isocyanate to form urea bonds, and hydrogen bonds are formed between the urea bonds in the polymer system, and 3,4-diaminofurazole and Zn 2+ The formation of metal coordination bonds enhances the interaction between molecular chains, making the caulking agent have excellent mechanical properties. Therefore, the prepared caulking agent has excellent anti-fouling properties and significantly improved mechanical properties.

[0090] In Comparative Example 1, since 1,2-benzisothiazol-3-one was not added, it can be seen from Table 1 that the antifouling performance is significantly reduced. This may be because 1,2-benzisothiazol-3-one is a common antifouling active substance. Without 1,2-benzisothiazol-3-one, the antifouling performance will be significantly reduced; in Example 2, since 3,4-diaminofurazan was not added, it can be seen from Table 1 that the mechanical properties and hydrophobic properties are significantly reduced. This may be because the 3,4-diaminofurazan chain extender is lost, the modified amino silicone oil prepolymer cannot form a metal coordination bond, the urea bond content in the prepolymer is also reduced, the hydrogen bonds formed between the urea bonds are also reduced, and the interaction between the hydrogen bonds and the coordination bonds is also reduced, which leads to a decrease in the mechanical properties of the seam beautifying agent. At the same time, the water contact angle is also significantly reduced, close to 90°, which makes the hydrophobic performance of the seam beautifying agent also decrease; in Comparative Example 3, since ZnCl2 was not added, it can be seen from Table 1 that the hydrophobic performance and mechanical properties are reduced. This may be because the loss of Zn 2+It cannot form metal coordination bonds, the modified aminosilicone prepolymer molecules are relatively loose and no longer have a network structure. Water molecules can easily enter the coating, and the mechanical properties will also decrease slightly. Since no modified aminosilicone prepolymer is added to comparative agent 4, it can be seen from Table 1 that the antifouling performance is significantly reduced, the water contact angle is also reduced, but the mechanical properties are slightly increased. This may be due to the lack of 1,2-benzisothiazol-3-one antifouling active substance, which reduces the antifouling performance. The decrease in hydrophobicity may be due to the loss of aminopropyl polydimethylsiloxane. Since the Si-O-Si bond energy in aminopropyl polydimethylsiloxane is small and the film-forming property is good, the surface of the coating formed is smoother. Without aminopropyl polydimethylsiloxane, the hydrophobicity of the seam beautifier decreases, and the mechanical properties are slightly increased. This may be because there is no low surface energy silicon segment introduced into the polyaspartic acid ester, which may increase the mechanical properties of the seam beautifier, but the increase effect is not very obvious.

[0091] It should be understood by those skilled in the art that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0092] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A bio-based polyurea seam beautifying agent, characterized in that: The invention is prepared from the following raw materials in parts by weight: 3-8 parts of modified amino silicone oil prepolymer, 15-20 parts of polyether polyol prepolymer, 50-60 parts of polyaspartic acid ester, 15-20 parts of hydrophobic glass microbeads, 45-50 parts of deionized water, and 3-5 parts of antibacterial agent; The modified amino silicone oil prepolymer is prepared from 1,2-benzisothiazol-3-one, isophorone diisocyanate, amino silicone oil, 3,4-diaminofurazole and ZnCl2.

2. The bio-based polyurea seam beautifying agent according to claim 1, characterized in that: The amino silicone oil is aminopropyl polydimethylsiloxane.

3. The bio-based polyurea seam beautifying agent according to claim 1, characterized in that: The particle size of the hydrophobic glass microbeads is 150-300 meshes.

4. The bio-based polyurea seam beautifying agent according to claim 1, characterized in that: The antibacterial agent is any one of nano zinc oxide and nano silver.

5. The bio-based polyurea seam beautifying agent according to claim 1, characterized in that: The preparation method of the modified amino silicone oil prepolymer is as follows: Step A1. Under room temperature, add isophorone diisocyanate solution dropwise to 1,2-benzisothiazol-3-one solution, and react at 60-70°C for 3-5h to obtain a mixed solution A; Step A2. Add the mixed solution A dropwise into the aminopropyl polydimethylsiloxane solution and react at room temperature for 3-5 hours to obtain a prepolymer B; Step A3. Add 3,4-diaminofurazole to prepolymer B, react at 50-70°C for 3-5 hours, add ZnCl2, and stir for 1-2 hours to obtain a modified amino silicone oil prepolymer.

6. The bio-based polyurea seam-beautifying agent according to claim 5, characterized in that: The isophorone diisocyanate solution in step A1 is prepared by dissolving 7-10 g of isophorone diisocyanate in 60-80 mL of tetrahydrofuran; The 1,2-benzisothiazol-3-one solution in step A1 is obtained by dissolving 5-8 g of 1,2-benzisothiazol-3-one in 40-50 mL of tetrahydrofuran; The volume ratio of the isophorone diisocyanate solution and the 1,2-benzisothiazol-3-one solution in step A1 is 60-80:40-50; The aminopropyl polydimethylsiloxane solution in step A2 is 40-45 g of aminopropyl polydimethylsiloxane dissolved in 400-40 mL of tetrahydrofuran.

7. The bio-based polyurea seam beautifying agent according to claim 5, characterized in that: The mass ratio of 3,4-diaminofurazole, prepolymer B and ZnCl2 in step A3 is 1-1.2:10-12:0.3-0.

5.

8. The bio-based polyurea seam beautifying agent according to claim 1, characterized in that: The preparation method of the polyether polyol type prepolymer is as follows: Mix polytetrahydrofuran diol, polypropylene glycol and dibutyltin dilaurate, stir at 100-105°C for 30-40 minutes and then cool to room temperature, drop isophorone diisocyanate solution into the mixed solution, and after the dropwise addition is completed, heat the system to 80-85°C and react for 2-3 hours to obtain a polyether polyol prepolymer.

9. The bio-based polyurea seam beautifying agent according to claim 8, characterized in that: The dosage ratio of the polytetrahydrofuran diol, polypropylene glycol, dibutyltin dilaurate, and isophorone diisocyanate solution is 40-45 g: 60-65 g: 0.1-0.3 g: 450-480 mL; The isophorone diisocyanate solution is prepared by dissolving 45-50 g of isophorone diisocyanate in 450-480 mL of tetrahydrofuran.

10. The method for preparing the bio-based polyurea seam beautifying agent according to any one of claims 1 to 9, characterized in that: The following steps are involved: The modified amino silicone oil prepolymer and the polyether polyol prepolymer are mixed in a rotary and revolving mixer at a speed of 2000 r / min for 2-5 minutes, and then polyaspartic acid ester, hydrophobic glass microbeads and antibacterial agent are added. After stirring for 5-7 minutes, degassing is carried out at 2000 r / min for 1-2 minutes. The mixture is placed in a vacuum oven and dried at 50°C for 3-5 hours. Deionized water is added and mixed evenly to obtain a bio-based polyurea seam beautifying agent.

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