Environment-friendly bio-based radix asparagi polyurea sealant and preparation method thereof

Abstract

The invention belongs to the technical field of sealant, and relates to an environment-friendly bio-based aspartic polyurea sealant and a preparation method thereof.The sealant comprises a component A and a component B. The component A comprises, by weight, 50-70 parts of polyaspartic acid resin, 0.1-0.4 part of a defoaming agent, 0.3-0.8 part of a dispersing agent, 30-50 parts of filler and 2-4 parts of a plasticizer; the component B is prepared from the following components in parts by weight: 85 to 95 parts of bio-based modified isocyanate prepolymer, 5 to 10 parts of filler, 0.1 to 0.4 part of defoaming agent and 0.3 to 0.8 part of dispersing agent. The environment-friendly bio-based radix asparagi polyurea sealant not only has the characteristics of high tensile strength and elongation at break, but also has the characteristics of yellowing resistance, low shrinkage rate, scratch resistance, good waterproofness and the like, is a safe, environment-friendly, green and renewable sealant which does not contain harmful substances such as formaldehyde, benzene and the like, is higher in environmental protection grade and safer, is safe and harmless to human bodies and the environment, and has a wide application prospect. VOC is ultralow, and large-area construction is free of peculiar smell.

Description

Technical Field

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

[0002] As people's living standards continue to improve, the requirements for the aesthetics, comfort and safety of living are getting higher and higher. Among them, the grouting agent, which is indispensable for tile laying, is also constantly updated.

[0003] Compared with traditional seam beautifiers, bio-based seam beautifiers have the following advantages:

[0004] Environmental performance: Bio-based caulking agents are based on bio-based materials, which are derived from renewable resources and have green and environmentally friendly characteristics. Traditional caulking agents contain more chemical components, which have a greater impact on the environment and human health. In contrast, the environmental performance of bio-based caulking agents helps reduce indoor air pollution and provide a healthier living environment.

[0005] Construction performance: The construction performance of bio-based caulking agents is generally better. They are easier to mix evenly and have a moderate curing speed, making it easier for construction workers to operate.

[0006] In addition, bio-based caulking agents have stronger adhesion and can better bond with building materials such as tiles, reducing the risk of falling off.

[0007] In summary, bio-based caulking agents are superior to traditional caulking agents in terms of environmental performance and construction performance. Therefore, it is particularly important to develop bio-based caulking agents with better performance. Summary of the invention

[0008] In view of the above-mentioned prior art, the present invention provides an environmentally friendly bio-based asparagus polyurea seam beautifying agent and a preparation method thereof. The specific technical scheme is as follows:

[0009] The first object of the present invention is to provide an environmentally friendly bio-based asparagus polyurea seam beautifying agent, comprising component A and component B, which are calculated by weight.

[0010] Component A includes:

[0011] 50-70 parts of polyaspartic acid resin, 0.1-0.4 parts of defoamer, 0.3-0.8 parts of dispersant, 30-50 parts of filler, 2-4 parts of plasticizer;

[0012] Component B includes:

[0013] 65-95 parts of bio-based modified isocyanate prepolymer, 5-10 parts of filler, 0.1-0.4 parts of defoamer, and 0.3-0.8 parts of dispersant; the bio-based modified isocyanate prepolymer is prepared from 30-50 parts of isocyanate, 40-70 parts of bio-based polyol, and 1-2 parts of catalyst;

[0014] The mass ratio of the component A to the component B is 1:0.8-1.2.

[0015] The present invention modifies bio-based polyol and isocyanate to prepare a novel bio-based modified isocyanate prepolymer, and utilizes the isocyanate group of the bio-based modified isocyanate prepolymer to react with the active hydrogen of polyaspartic acid resin (such as hydrogen on the amine group) to obtain an environmentally friendly bio-based aspartic polyurea seam beautifying agent, which not only has the characteristics of high tensile strength and elongation at break, but also has the characteristics of yellowing resistance, low shrinkage, scratch resistance, good water resistance, etc. It is a safe, environmentally friendly, green and renewable seam beautifying agent with a higher environmental protection level and safer than any harmful substances such as formaldehyde and benzene, is safe and harmless to human body and environment, has ultra-low VOC, and has no odor when applied to large areas.

[0016] Furthermore, the preparation method of the bio-based modified isocyanate prepolymer is to add isocyanate, bio-based polyol and catalyst into a reaction kettle, and react at a reaction temperature of 100° C. to 130° C. for 6 h to 10 h.

[0017] Further, the isocyanate is one or more of dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, biuret triisocyanate, and hexamethylene triisocyanate;

[0018] The bio-based polyol is one or more of soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, polylactic acid polyol, castor oil polyol, olive oil polyol, sugar polyol, bio-based glycerol, and bio-based ethylene glycol;

[0019] The catalyst is organic bismuth or organic tin.

[0020] Furthermore, the polyaspartic acid resin is one or more of W420, W330, W520, W220, W2850, W5401, W5402, W5405, F420, F330, F520, F220, and F2850.

[0021] Furthermore, the defoaming agent is a phosphate ester or organosilicon compound defoaming agent.

[0022] Furthermore, the dispersant is a BYK series dispersant.

[0023] Furthermore, the filler is one or more of titanium dioxide, fumed silica, iron oxide pigment, and pearlescent powder.

[0024] Furthermore, the plasticizer is one or more of ATBC, DINP, EFAME, DOP, and DOTP.

[0025] The second object of the present invention is to provide a method for preparing the above-mentioned environmentally friendly bio-based asparagus polyurea seam beautifying agent, comprising the following steps:

[0026] Preparation of component A:

[0027] A1: Stir polyaspartic acid resin, 0.1-0.3 parts of defoamer and dispersant at 2000-2500 rpm for 25-30 minutes;

[0028] A2: Add filler and stir at 2500 rpm to 3500 rpm for 50 to 100 minutes;

[0029] A3: Add the remaining defoamer and plasticizer, and stir at a speed of 700 rpm to 1500 rpm for 25 to 30 minutes to obtain component A;

[0030] Preparation of component B:

[0031] B1: Stir the bio-based modified isocyanate prepolymer and dispersant at a speed of 2000 rpm to 2500 rpm for 25 to 30 minutes;

[0032] B2: Add filler and stir at 2500 rpm to 3500 rpm for 50 to 100 minutes;

[0033] B3: Add defoaming agent and stir at a rotation speed of 700 rpm to 1500 rpm for 25 to 30 minutes to obtain component B.

[0034] The beneficial effects of the present invention are:

[0035] The invention uses a homemade renewable and environmentally friendly bio-based modified isocyanate prepolymer to react with a polyaspartic acid resin to prepare an environmentally friendly bio-based aspartate polyurea seam beautifying agent, which is superior to ordinary aspartate polyurea seam beautifying agents in terms of operating time, safety and environmental protection; and the production process is simple and the raw materials are green and environmentally friendly. DETAILED DESCRIPTION

[0036] The principles and features of the present invention are described below in conjunction with embodiments. The embodiments are only used to explain the present invention and are not used to limit the scope of the present invention.

[0037] Embodiment 1:

[0038] Preparation of bio-based modified isocyanate prepolymer 1:

[0039] By weight, 50 parts of castor oil bio-based polyol, 34 parts of isophorone diisocyanate, 15 parts of 4,4'-dicyclohexylmethane diisocyanate, and 1 part of organic bismuth were added into a reactor, and reacted at a reaction temperature of 120° C. for 8 hours to obtain a bio-based modified isocyanate prepolymer 1.

[0040] The preparation of the environmentally friendly bio-based asparagus polyurea seam beautifying agent includes component A and component B with a mass ratio of 1:1:

[0041] Preparation of component A:

[0042] A1: By weight, 50 parts of W420 polyaspartic acid resin, 0.1 parts of BYK-066N defoamer, and 0.3 parts of BYK110 dispersant were stirred at 2000 rpm for 30 minutes;

[0043] A2: Add 10 parts of fumed silica, 20 parts of titanium dioxide, and 2 parts of iron oxide pigment, and stir at 3000 rpm for 60 minutes;

[0044] A3: Add 0.1 parts of BYK-066N defoamer and 2 parts of DOTP plasticizer, and stir at 1000 rpm for 25 minutes to obtain component A.

[0045] Preparation of component B:

[0046] B1: By weight, 70 parts of bio-based modified isocyanate prepolymer 1 and 0.3 parts of BYK110 dispersant were stirred at 2000 rpm for 25 minutes;

[0047] B2: Add 5 parts of fumed silica and stir at 3000 rpm for 60 minutes;

[0048] B3: Add 0.1 parts of BYK-066N defoamer and stir at 1000 rpm for 25 minutes to obtain component B.

[0049] Embodiment 2:

[0050] Preparation of bio-based modified isocyanate prepolymer II:

[0051] By weight, 55 parts of soybean oil bio-based polyol, 29 parts of isophorone diisocyanate, 15 parts of 4,4'-dicyclohexylmethane diisocyanate, and 1 part of organic bismuth were added into a reactor and reacted at a reaction temperature of 120° C. for 8 hours to obtain a bio-based modified isocyanate prepolymer II.

[0052] The preparation of the environmentally friendly bio-based asparagus polyurea seam beautifying agent includes component A and component B with a mass ratio of 1:1:

[0053] Preparation of component A:

[0054] A1: By weight, 50 parts of W420 polyaspartic acid resin, 0.1 parts of BYK-066N defoamer, and 0.3 parts of BYK110 dispersant were stirred at 2000 rpm for 30 minutes;

[0055] A2: Add 15 parts of fumed silica, 15 parts of titanium dioxide, and 2 parts of iron oxide pigment, and stir at 3000 rpm for 60 minutes;

[0056] A3: Add 0.1 parts of BYK-066N defoamer and 3 parts of DOTP plasticizer, and stir at 1000 rpm for 25 minutes to obtain component A.

[0057] Preparation of component B:

[0058] B1: By weight, 70 parts of bio-based modified isocyanate prepolymer II and 0.3 parts of BYK110 dispersant were stirred at 2000 rpm for 25 minutes;

[0059] B2: Add 5 parts of fumed silica and stir at 3000 rpm for 60 minutes;

[0060] B3: Add 0.1 parts of BYK-066N defoamer and stir at 1000 rpm for 25 minutes to obtain component B.

[0061] Embodiment 3:

[0062] Preparation of bio-based modified isocyanate prepolymer III:

[0063] By weight, 60 parts of cashew nut shell oil bio-based polyol, 29 parts of isophorone diisocyanate, 10 parts of 4,4'-dicyclohexylmethane diisocyanate, and 1 part of organic bismuth were added into a reactor and reacted at a reaction temperature of 120°C for 8 hours to obtain bio-based modified isocyanate prepolymer three.

[0064] The preparation of the environmentally friendly bio-based asparagus polyurea seam beautifying agent includes component A and component B with a mass ratio of 1:1:

[0065] Preparation of component A:

[0066] A1: By weight, 50 parts of W420 polyaspartic acid resin, 0.1 parts of BYK-066N defoamer, and 0.3 parts of BYK110 dispersant were stirred at 2000 rpm for 30 minutes;

[0067] A2: Add 15 parts of fumed silica, 15 parts of titanium dioxide, and 2 parts of iron oxide pigment, and stir at 3000 rpm for 60 minutes;

[0068] A3: Add 0.1 parts of BYK-066N defoamer and 3 parts of DOTP plasticizer, and stir at 1000 rpm for 25 minutes to obtain component A.

[0069] Preparation of component B:

[0070] B1: By weight, 70 parts of bio-based modified isocyanate prepolymer III and 0.3 parts of BYK110 dispersant were stirred at 2000 rpm for 25 minutes;

[0071] B2: Add 5 parts of fumed silica and stir at 3000 rpm for 60 minutes;

[0072] B3: Add 0.1 parts of BYK-066N defoamer and stir at 1000 rpm for 25 minutes to obtain component B.

[0073] Comparative Example 1:

[0074] Traditional caulking agent: Hanjiang Asparagus Polyurea Caulking Agent produced by Shandong Zhongzhuo Building Materials Co., Ltd., which has good sales and effects in the market.

[0075] Performance Test:

[0076] 1. Surface drying time test: The above-mentioned Examples 1 to 3 and the traditional seam beautifying agent were subjected to a surface drying time test, and the test method was carried out in accordance with GB / T 1968-2020 "Determination of Drying Time of Paint Film and Putty Film".

[0077] 2. Yellowing resistance test: The above-mentioned Examples 1 to 3 and the traditional caulking agent were respectively filled into the gaps of outdoor tiles, and the yellowing was observed after 6 months.

[0078] 3. Wear resistance test: The above-mentioned Examples 1 to 3 and the traditional seam beautifier were subjected to a wear resistance test. The test method was carried out in accordance with GB / T1689-1998 "Determination of wear resistance of vulcanized rubber". The thickness of the prepared sample was 2 mm and the curing time was 48 hours.

[0079] 4. Scratch resistance test: The above-mentioned Examples 1 to 3 and the traditional seam beautifier were subjected to a scratch resistance test. The test method was carried out in accordance with GB / T 9279-2007 "Paint and Varnish Scratch Test". The film thickness of the prepared sample was 1.5 mm, and the load during the test was 10 kg.

[0080] 5. Shrinkage test: The above-mentioned Examples 1 to 3 and the traditional caulking agent were respectively filled into the tile gaps with a depth of 1 cm and a width of 5 mm, and the caulking effect was observed after curing for 24 hours.

[0081] 6. Tensile strength test: The tensile strength test of the above-mentioned Examples 1 to 3 and the traditional seam beautifying agent was carried out in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0082] 7. Elongation at break test: The tensile strength test of the above-mentioned Examples 1 to 3 and the traditional seam beautifier was carried out in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0083] 8. Elongation at break test: The above-mentioned Examples 1 to 3 and the traditional seam beautifier were subjected to flexibility test, and the test method was carried out in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0084] 9. Flexibility test: The above-mentioned Examples 1 to 3 and the traditional seam beautifying agent were subjected to a flexibility test, and samples were prepared in accordance with GB / T1731-2020 "Determination of Flexibility of Paint Film and Putty Film", and the test temperature was 0°C.

[0085] 10. Shore hardness test: The flexibility of the above-mentioned Examples 1 to 3 and the traditional caulking agent was tested in accordance with GB / T 2411-2008 "Determination of indentation hardness of plastics and hard rubber using a durometer".

[0086] The results of the above performance tests are shown in Table 1:

[0087] Table 1 Performance test results of traditional seam beautifying agents in Examples 1 to 3 and Comparative Example 1

[0088] index Example 1 Example 2 Example 3 Comparative Example 1 Appearance White White White White Operation time, min 40 43 39 20 Yellowing No yellowing No yellowing No yellowing No yellowing Wear resistance, mg <1 mg <1 mg <1 mg <1 mg Scratch resistance No scratches No scratches No scratches No scratches Contractility No shrinkage No shrinkage No shrinkage No shrinkage Tensile strength, MPa 20 18 19 17 Elongation at break, % 109 106 110 97 Flexibility pass pass pass pass Shore Hardness 79 83 78 77

[0089] It can be seen from the test data in Table 1 that the environmentally friendly bio-based asparagus polyurea caulking agent prepared by using the homemade bio-based modified isocyanate prepolymer as the raw material of the present invention has the characteristics of high tensile strength and high elongation at break, and is more environmentally friendly than the asparagus polyurea caulking agent of Comparative Example 1, and the present invention also solves the problem that the raw materials are not environmentally friendly enough when preparing the isocyanate prepolymer. The performance of the environmentally friendly bio-based asparagus polyurea caulking agent of the present invention is closely related to the raw materials and process parameters. Changing the raw materials or process parameters will lead to a decrease in the performance of the caulking agent.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An environmentally friendly bio-based asparagus polyurea seam beautifying agent, characterized in that: Including component A and component B, by weight, Component A includes: 50-70 parts of polyaspartic acid resin, 0.1-0.4 parts of defoamer, 0.3-0.8 parts of dispersant, 30-50 parts of filler, 2-4 parts of plasticizer; Component B includes: 65-95 parts of bio-based modified isocyanate prepolymer, 5-10 parts of filler, 0.1-0.4 parts of defoamer, and 0.3-0.8 parts of dispersant; the bio-based modified isocyanate prepolymer is prepared from 30-50 parts of isocyanate, 40-70 parts of bio-based polyol, and 1-2 parts of catalyst; The mass ratio of the component A to the component B is 1:0.8-1.

2.

2. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The preparation method of the bio-based modified isocyanate prepolymer comprises adding isocyanate, bio-based polyol and catalyst into a reaction kettle, and reacting at a reaction temperature of 100° C. to 130° C. for 6 h to 10 h.

3. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The isocyanate is one or more of dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, methylcyclohexyl diisocyanate, biuret triisocyanate, and hexamethylene triisocyanate.

4. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The bio-based polyol is one or more of soybean oil polyol, palm oil polyol, cashew nut shell oil polyol, polylactic acid polyol, castor oil polyol, olive oil polyol, sugar polyol, bio-based glycerol, and bio-based ethylene glycol.

5. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The catalyst is organic bismuth or organic tin.

6. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The polyaspartic acid resin is one or more of W420, W330, W520, W220, W2850, W5401, W5402, W5405, F420, F330, F520, F220, and F2850.

7. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The defoamer is a phosphate ester or organosilicon compound defoamer; the dispersant is a BYK series dispersant.

8. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The filler is one or more of titanium dioxide, fumed silica, iron oxide pigment and pearlescent powder.

9. The environmentally friendly bio-based asparagine polyurea seam beautifying agent according to claim 1, characterized in that: The plasticizer is one or more of ATBC, DINP, EFAME, DOP and DOTP.

10. A method for preparing the environmentally friendly bio-based asparagine polyurea seam beautifying agent according to any one of claims 1 to 9, characterized in that: The following steps are included: Preparation of component A: A1: Stir polyaspartic acid resin, 0.1-0.3 parts of defoamer and dispersant at 2000-2500 rpm for 25-30 minutes; A2: Add filler and stir at 2500 rpm to 3500 rpm for 50 to 100 minutes; A3: Add the remaining defoamer and plasticizer, and stir at a speed of 700 rpm to 1500 rpm for 25 to 30 minutes to obtain component A; Preparation of component B: B1: Stir the bio-based modified isocyanate prepolymer and dispersant at a speed of 2000 rpm to 2500 rpm for 25 to 30 minutes; B2: Add filler and stir at 2500 rpm to 3500 rpm for 50 to 100 minutes; B3: Add defoaming agent and stir at a rotation speed of 700 rpm to 1500 rpm for 25 to 30 minutes to obtain component B.