Modified polyurea sealant with high tensile strength and bonding strength and preparation method thereof

Abstract

The invention belongs to the technical field of seam beautifying agents, and relates to a modified polyurea seam beautifying agent with high tensile strength and bonding strength and a preparation method of the modified polyurea seam beautifying agent. The component A is prepared from 20 to 100 parts of modified polyaspartic acid resin, 20 to 50 parts of polyaspartic acid resin, 5 to 60 parts of filler, 4 to 6 parts of color paste, 0.1 to 0.5 part of defoaming agent, 0.1 to 0.8 part of dispersing agent and 1 to 4 parts of anti-wear agent; the component B is prepared from 10 to 50 parts of hexamethylene diisocyanate tripolymer, 0 to 30 parts of isocyanate, 45 to 75 parts of isocyanate prepolymer, 5 to 60 parts of filler, 0.1 to 0.4 part of defoaming agent and 0.1 to 0.8 part of dispersing agent; the mass ratio of the component A to the component B is 1: (1.0-1.2). The modified polyurea sealant has high tensile strength and high bonding strength, and also has the characteristics of excellent scratch resistance, acid and alkali resistance, yellowing resistance, low shrinkage, mildew resistance and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of seam beautifying agents, and in particular relates to a modified polyurea seam beautifying agent with high tensile strength and bonding strength and a preparation method thereof. Background Art

[0002] In recent decades, the booming real estate industry has greatly promoted the prosperity of the housing decoration industry, and residents have increasingly pursued the beauty, comfort and safety of their living environment. Against this background, the caulking materials that are indispensable in tile paving have also undergone a significant evolution, starting from the initial inorganic white cement grout, through the innovation of the second generation of grouts, to the third generation of epoxy grouts that are widely used today.

[0003] The first generation of caulking agents, which mainly consist of cement, calcium carbonate powder, talcum powder and rubber powder, have the disadvantages of being prone to blackening and mildew, bacterial breeding, single color and limited waterproof performance. The third generation of epoxy caulking agents that came out later significantly improved water resistance and mildew resistance, and also had anti-scratch performance and a variety of color options, greatly meeting market demand. However, it is not perfect either, and faces challenges such as insufficient antioxidant capacity, poor UV resistance, possible shrinkage and cracking after long-term use, and limited construction in winter.

[0004] At present, although asparagus polyurea caulking agent is gradually gaining favor among consumers as a new decorative material with many advantages in the market, such as excellent weather resistance, wear resistance, good elastic recovery and rich color selection, it still faces challenges that cannot be ignored in the actual application process. Among them, the most significant problem is that this type of caulking agent has poor bonding strength to the tile surface.

[0005] Specifically, although the asparagus polyurea grouting agent can basically meet the needs of filling and beautifying the gaps between tiles during the initial construction, after a period of time, especially the extreme temperature changes in summer and winter, the bonding strength between the asparagus polyurea grouting agent and the tiles will often decrease significantly, causing the edges of the grouting agent to lift up or even fall off as a whole. This not only seriously affects the overall aesthetics of the home environment, but also brings users the trouble of frequent repairs, greatly reducing users' satisfaction and trust in the asparagus polyurea grouting agent product.

[0006] Therefore, improving the bonding strength of asparagus polyurea caulking agent to tiles and ensuring that it can maintain a stable bonding state under various environmental conditions has become a key technical problem that needs to be urgently solved in the current industry. Summary of the invention

[0007] In view of the deficiencies of the above-mentioned prior art, the present invention provides a modified polyurea seam beautifying agent with high tensile strength and bonding strength and a preparation method thereof. The specific technical scheme is as follows:

[0008] The first object of the present invention is to provide a modified polyurea caulking agent with high tensile strength and bonding strength, including component A and component B. By weight,

[0009] Component A includes:

[0010] 20-100 parts of modified polyaspartic acid resin, 20-50 parts of polyaspartic acid resin, 5-60 parts of filler, 4-6 parts of color paste, 0.1-0.5 parts of defoamer, 0.1-0.8 parts of dispersant, 1-4 parts of anti-wear agent;

[0011] The modified polyaspartic acid resin is prepared from 6-40 parts of epoxy resin, 60-100 parts of polyaspartic acid resin, and 0-1 part of catalyst;

[0012] Component B includes:

[0013] 10-50 parts of hexamethylene diisocyanate trimer, 0-30 parts of isocyanate, 45-75 parts of isocyanate prepolymer, 5-60 parts of filler, 0.1-0.4 parts of defoamer, 0.1-0.8 parts of dispersant;

[0014] The isocyanate prepolymer is prepared from 20-80 parts of polyol, 20-80 parts of isocyanate, 0-20 parts of plasticizer, and 0.1-1.0 parts of catalyst;

[0015] The mass ratio of component A to component B is 1:1.0-1.2.

[0016] The present invention modifies polyaspartic acid resin with epoxy resin, and then reacts the modified polyaspartic acid resin with the curing agent component to prepare a new type of modified aspartic polyurea caulking agent. The modified polyurea caulking agent prepared by the preparation method of the present invention has the characteristics of high tensile strength, high bonding strength, excellent scratch resistance, acid and alkali resistance, yellowing resistance, low shrinkage, and mildew resistance.

[0017] Furthermore, the preparation method of the modified polyaspartic acid resin is to add epoxy resin, polyaspartic acid resin, and catalyst into a reaction kettle, and react at a reaction temperature of 60°C-110°C for 5h-24h.

[0018] The reaction example of the modified polyaspartic acid resin is as follows:

[0019]

[0020] Among them, the groups represented by R, X, and R1 are determined by the epoxy resin and polyaspartic acid resin used.

[0021] Further, the epoxy resin is one or more of BE113, BE114, BE115, BE186, BE186EL, BE188, BE188EL, BE501, BE502, BE502H, BE503L, BE503, BE504, BE507, BE509, BFE-170, BFE-235, BFE-235L, BFE-283, TFE2000, TFE1250, AGE, BDGE, CDGE, TMP7300, HBE7210.

[0022] Further, the polyaspartic resin is one or more of W520, W420, W330, W2850, F220, F421, F423, F524, F2850H-2, F2872, F157, F221.

[0023] Further, the method for preparing the isocyanate prepolymer is to add polyol, isocyanate, plasticizer, and catalyst into a reaction kettle, and react at a reaction temperature of 80°C to 120°C for 5h to 24h to obtain it.

[0024] The reaction example of the isocyanate prepolymer is as follows:

[0025]

[0026] Among them, the groups represented by R2 and R3 are determined by the polyol and isocyanate used.

[0027] Further, the polyol is one or more of polyether polyol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol.

[0028] Further, the isocyanate is one or more of isophorone diisocyanate, 2,2,4-trimethylhexane diisocyanate, dicyclohexylmethane diisocyanate, naphthalene-1,5-diisocyanate, and hexamethylene diisocyanate.

[0029] Further, the plasticizer is one or more of ATBC, DINP, EFAME, DOP, and DTOP.

[0030] Further, the catalyst is one or more of organic zinc, organic tin, organic bismuth, and triethylenediamine.

[0031] Further, the defoamer is a phosphate ester or silicone compound defoamer.

[0032] Further, the dispersant is a BYK series dispersant.

[0033] Furthermore, the filler is one or more of fumed silica, titanium dioxide, iron oxide pigment and pearlescent powder.

[0034] Furthermore, the anti-wear agent is glass powder; the color paste is a conventional brand of color paste on the market and can be various colors.

[0035] The second object of the present invention is to provide a method for preparing the modified polyurea seam beautifying agent with high tensile strength and bonding strength, comprising the following steps:

[0036] Preparation of component A:

[0037] A1: Stir the modified polyaspartic acid resin, polyaspartic acid resin and dispersant at a speed of 1000 rpm to 2500 rpm for 10 to 30 minutes;

[0038] A2: Add filler and color paste, and stir at 1000rpm-2500rpm for 10-30 minutes;

[0039] A3: Add defoaming agent and anti-wear agent, and stir at a speed of 700 rpm to 1500 rpm for 10 to 30 minutes to obtain component A;

[0040] Preparation of component B:

[0041] B1: Stir hexamethylene diisocyanate trimer, isocyanate prepolymer, isocyanate and dispersant at a speed of 1000 rpm to 2500 rpm for 10 to 30 minutes;

[0042] B2: Add filler and stir at 1000 rpm to 2500 rpm for 10 to 30 minutes;

[0043] B3: Add defoaming agent and stir at a rotation speed of 700 rpm to 1500 rpm for 10 to 30 minutes to obtain component B.

[0044] The present invention has the following beneficial effects:

[0045] The modified polyurea caulking agent prepared by the present invention through self-made modified polyaspartic acid resin and isocyanate prepolymer solves the problem that the bonding strength between the current polyurea caulking agent and the ceramic tile will be significantly reduced after experiencing the extreme temperature changes in summer and winter, thereby causing the edge of the caulking agent to warp or even fall off as a whole; the modified polyurea caulking agent prepared by the present invention has high tensile strength and high bonding strength, and also has excellent scratch resistance, acid and alkali resistance, yellowing resistance, low shrinkage, mildew resistance and the like. DETAILED DESCRIPTION

[0046] The principles and features of the present invention will be described below in conjunction with embodiments. The embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0047] Example 1:

[0048] Preparation of modified polyaspartic acid resin A:

[0049] By weight, 100 parts of W420 polyaspartic acid resin (Yantai Wanshun New Materials Co., Ltd.), 7.2 parts of BNE200 epoxy resin, and 0.1 part of organic bismuth catalyst were added to a reaction kettle and reacted at a reaction temperature of 70°C for 12 hours to obtain modified polyaspartic acid resin A.

[0050] Preparation of modified polyaspartic acid resin B:

[0051] By weight, 100 parts of W330 polyaspartic acid resin (Yantai Wanshun New Materials Co., Ltd.), 12.6 parts of BNE200 epoxy resin, and 0.1 part of organic bismuth catalyst were added to a reaction kettle and reacted at a reaction temperature of 70°C for 12 hours to obtain modified polyaspartic acid resin B.

[0052] Preparation of isocyanate prepolymer A:

[0053] By weight, 50 parts of C2010 polyether polyol, 41 parts of isophorone diisocyanate, and 0.1 part of organic bismuth catalyst were added to a reaction kettle and reacted at a reaction temperature of 90°C for 10 hours to obtain isocyanate prepolymer A.

[0054] Preparation of modified polyurea joint sealer with high tensile strength and bonding strength, including component A and component B with a mass ratio of 1:1:

[0055] Preparation of component A:

[0056] A1: By weight, 70 parts of modified polyaspartic acid resin A, 30 parts of modified polyaspartic acid resin B, and 0.1 part of BYK110 dispersant were stirred at a speed of 1500 rpm for 15 minutes;

[0057] A2: 8 parts of fumed silica and 4 parts of titanium white paste were added and stirred at a speed of 2000 rpm for 20 minutes;

[0058] A3: 0.1 part of BYK 012 defoamer and 2 parts of glass powder were added and stirred at a speed of 1500 rpm for 15 minutes to obtain component A.

[0059] Preparation method of component B:

[0060] 1) By weight, 30 parts of hexamethylene diisocyanate trimer, 70 parts of isocyanate prepolymer A, and 0.1 part of BYK110 dispersant are stirred at a speed of 1500 rpm for 15 minutes;

[0061] 2) 6 parts of fumed silica are added and stirred at a speed of 2000 rpm for 20 minutes;

[0062] 3) 0.1 part of BYK 012 defoamer is added and stirred at a speed of 1500 rpm for 15 minutes to obtain Component B.

[0063] Example 2:

[0064] Preparation of modified polyaspartic acid resin C:

[0065] By weight, 100 parts of W420 polyaspartic acid resin (Yantai Wanshun New Materials Co., Ltd.), 14.4 parts of BNE200 epoxy resin, and 0.1 part of organic bismuth catalyst are added to the reaction kettle and reacted at a reaction temperature of 70 °C for 12 h to obtain modified polyaspartic acid resin C.

[0066] Preparation of isocyanate prepolymer B:

[0067] By weight, 63 parts of C2010 polyether polyol, 37 parts of isophorone diisocyanate, and 0.1 part of organic bismuth catalyst are added to the reaction kettle according to the weight parts and reacted at a reaction temperature of 90 °C for 10 h to obtain isocyanate prepolymer B.

[0068] Preparation of modified polyurea joint beautifying agent with high tensile strength and bonding strength, including Component A and Component B with a mass ratio of 1:1:

[0069] Preparation of Component A:

[0070] 1) By weight, 70 parts of modified polyaspartic acid resin C, 30 parts of W330 polyaspartic acid resin, and 0.1 part of BYK110 dispersant are stirred at a speed of 1500 rpm for 15 minutes;

[0071] 2) 8 parts of fumed silica and 4 parts of titanium white paste are added and stirred at a speed of 2000 rpm for 20 minutes;

[0072] 3) 0.1 part of BYK 012 defoamer and 2 parts of glass powder are added and stirred at a speed of 1500 rpm for 15 minutes to obtain Component A.

[0073] Preparation of Component B:

[0074] 1) Weigh 40 parts of hexamethylene diisocyanate trimer, 55 parts of isocyanate prepolymer B, 5 parts of isophorone diisocyanate, and 0.1 part of BYK110 dispersant, and stir at a speed of 1500 rpm for 15 minutes;

[0075] 2) Add 6 parts of fumed silica and stir at a speed of 2000 rpm for 20 minutes;

[0076] 3) Add 0.1 part of BYK 012 defoamer and stir at a speed of 1500 rpm for 15 minutes to obtain Component B.

[0077] Example 3:

[0078] Preparation of modified polyaspartic acid resin C:

[0079] The same as in Example 2, which will not be elaborated here.

[0080] Preparation of modified polyaspartic acid resin D:

[0081] Weigh 100 parts of W520 polyaspartic acid resin (Yantai Wanshun New Materials Co., Ltd.), 12.5 parts of PNE177M80 epoxy resin, and 0.1 part of organic bismuth catalyst and add them to the reaction kettle. React at a reaction temperature of 80 °C for 15 h to obtain modified polyaspartic acid resin D.

[0082] Preparation of isocyanate prepolymer C:

[0083] Weigh 71 parts of C2020 polyether polyol, 29 parts of isophorone diisocyanate, and 0.1 part of organic bismuth catalyst according to the weight parts and add them to the reaction kettle. React at a reaction temperature of 90 °C for 15 h to obtain isocyanate prepolymer C.

[0084] Preparation of modified polyurea joint beautifying agent with high tensile strength and bonding strength, including Component A and Component B with a mass ratio of 1:1:

[0085] Preparation of Component A:

[0086] 1) Weigh 50 parts of modified polyaspartic acid resin C, 20 parts of modified polyaspartic acid resin D, 30 parts of W330 polyaspartic acid resin, and 0.1 part of BYK110 dispersant, and stir at a speed of 1500 rpm for 15 minutes;

[0087] 2) Add 8 parts of fumed silica and 4 parts of titanium white paste, and stir at a speed of 2000 rpm for 20 minutes;

[0088] 3) Add 0.1 part of BYK 012 defoamer and 2 parts of glass powder, and stir at a speed of 1500 rpm for 15 minutes to obtain Component A.

[0089] Preparation of Component B:

[0090] 1) By weight, 40 parts of hexamethylene diisocyanate trimer, 60 parts of isocyanate prepolymer C, 2 parts of isophorone diisocyanate, and 0.1 part of BYK110 dispersant are stirred at a speed of 1500 rpm for 15 minutes;

[0091] 2) Add 6 parts of fumed silica and stir at a speed of 2000 rpm for 20 minutes;

[0092] 3) Add 0.1 part of BYK 012 defoamer and stir at a speed of 1500 rpm for 15 minutes to obtain Component B.

[0093] Comparative Example 1:

[0094] Traditional caulking agent: The polyurea caulking agent of Weifang Ancai New Materials Co., Ltd. with good market sales and effects.

[0095] Performance testing:

[0096] 1. Surface drying time test: The surface drying time of Examples 1 - 3 and the traditional caulking agent above is tested. The test method is carried out in accordance with GB / T 1968 - 2020 "Determination of Drying Time of Paint Films and Putty Films".

[0097] 2. Abrasion resistance test: The abrasion resistance of Examples 1 - 3 and the traditional caulking agent above is tested. The test method is carried out in accordance with GB / T1689 - 1998 "Determination of Abrasion Resistance of Vulcanized Rubber". The thickness of the prepared specimen is 2 mm and it is cured for 48 h.

[0098] 3. Scratch resistance test: The scratch resistance of Examples 1 - 3 and the traditional caulking agent above is tested. The test method is carried out in accordance with GB / T 9279 - 2007 "Scratch Test for Paints and Varnishes". The thickness of the adhesive film of the prepared specimen is 1.5 mm and the load is 10 kg during the test.

[0099] 4. Shrinkage test: Examples 1 - 3 and the traditional caulking agent above are respectively filled into the tile joints with a depth of 1 cm and a width of 5 mm, and the caulking effect is observed after curing for 24 hours.

[0100] 5. Tensile strength test: The tensile strength of Examples 1 - 3 and the traditional caulking agent above is tested. The test method is carried out in accordance with GB / T 528 - 2009 "Determination of Tensile Stress - Strain Properties of Vulcanized Rubber or Thermoplastic Rubber".

[0101] 6. Elongation at break test: The above-mentioned Examples 1-3 and traditional joint sealants were subjected to tensile strength tests. The test method was carried out in accordance with GB / T 528-2009 "Rubber, vulcanized or thermoplastic - Determination of tensile stress - strain properties".

[0102] 7. Shore hardness test: The above-mentioned Examples 1-3 and traditional joint sealants were subjected to flexibility tests. The test method was carried out in accordance with GB / T 2411-2008 "Plastics and hard rubbers - Determination of indentation hardness by means of a durometer".

[0103] 8. Bond strength test: The above-mentioned Examples 1-3 and traditional joint sealants were subjected to bond strength tests. The test method was carried out in accordance with JC / T 547-2017 "Ceramic tile adhesives".

[0104] The results of the above performance tests are shown in Table 1:

[0105] Table 1 Performance test results of Examples 1-3 and Comparative Example 1

[0106] Index Example 1 Example 2 Example 3 Comparative Example 1 Appearance White White White White Surface drying time, min 20 25 25 15 Wear resistance, mg <1 mg <1 mg <1 mg 6 mg Scratch resistance No scratch No scratch No scratch Slightly scratched Shrinkage No shrinkage No shrinkage No shrinkage Slightly shrunk Tensile strength, Mpa 22 24 26 15 Elongation at break, % 43 36 35 20 Shore hardness 71 72 70 71 Adhesion strength, Mpa 18 22 21 9

[0107] It can be seen from the test data in Table 1 that the polyurea joint sealant prepared by using the self-made modified polyaspartic acid resin and modified isocyanate prepolymer as raw materials in the present invention has the characteristics of high tensile strength and high bond strength at the same time, and there are no obvious disadvantages in other performance indicators compared with the traditional joint sealant in Comparative Example 1. The performance of the modified polyurea joint sealant described in the present invention is closely related to the raw materials and process parameters. Changing the raw materials or process parameters will cause the performance of the joint sealant to decline.

[0108] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A modified polyurea caulking agent with high tensile strength and bonding strength, characterized in that, It includes Component A and Component B. By weight, Component A includes: 20 - 100 parts of modified polyaspartic acid resin, 20 - 50 parts of polyaspartic acid resin, 5 - 60 parts of filler, 4 - 6 parts of color paste, 0.1 - 0.5 part of defoamer, 0.1 - 0.8 part of dispersant, 1 - 4 parts of anti-wear agent; The modified polyaspartic acid resin is prepared from 6 - 40 parts of epoxy resin, 60 - 100 parts of polyaspartic acid resin, and 0 - 1 part of catalyst; Component B includes: 10 - 50 parts of hexamethylene diisocyanate trimer, 0 - 30 parts of isocyanate, 45 - 75 parts of isocyanate prepolymer, 5 - 60 parts of filler, 0.1 - 0.4 part of defoamer, 0.1 - 0.8 part of dispersant; The isocyanate prepolymer is prepared from 20 - 80 parts of polyol, 20 - 80 parts of isocyanate, 0 - 20 parts of plasticizer, and 0.1 - 1.0 part of catalyst; The mass ratio of Component A to Component B is 1:1.0 - 1.

2.

2. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, wherein, The preparation method of the modified polyaspartic acid resin is to add epoxy resin, polyaspartic acid resin, and catalyst into a reaction kettle, and react at a reaction temperature of 60°C - 110°C for 5h - 24h.

3. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, characterized in that The preparation method of the isocyanate prepolymer is to add polyol, isocyanate, plasticizer, and catalyst into a reaction kettle, and react at a reaction temperature of 80°C - 120°C for 5h - 24h to obtain it.

4. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, characterized in that, The epoxy resin is one or more of BE113, BE114, BE115, BE186, BE186EL, BE188, BE188EL, BE501, BE502, BE502H, BE503L, BE503, BE504, BE507, BE509, BFE - 170, BFE - 235, BFE - 235L, BFE - 283, TFE2000, TFE1250, AGE, BDGE, CDGE, TMP7300, HBE7210.

5. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, wherein The polyaspartic acid resin is one or more of W520, W420, W330, W2850, F220, F421, F423, F524, F2850H - 2, F2872, F157, F221.

6. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, characterized in that, The polyol is one or more of polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol; the isocyanate is one or more of isophorone diisocyanate, 2,2,4 - trimethylhexane diisocyanate, dicyclohexylmethane diisocyanate, naphthalene - 1,5 - diisocyanate, hexamethylene diisocyanate.

7. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, wherein The plasticizer is one or more of ATBC, DINP, EFAME, DOP, DTOP; the catalyst is one or more of organic zinc, organic tin, organic bismuth, triethylenediamine.

8. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, characterized in that, The defoamer is a phosphate ester - type or silicone compound - type defoamer; the dispersant is a BYK series dispersant.

9. The modified polyurea caulking agent with high tensile strength and bonding strength according to claim 1, wherein The filler is one or more of fumed silica, titanium dioxide, iron oxide pigment, and pearlescent powder; the anti - wear agent is glass powder.

10. A preparation method of a modified polyurea caulking agent with high tensile strength and bonding strength as described in any one of claims 1 to 9, characterized in that, It includes the following steps: Preparation of Component A: A1: Stir the modified polyaspartic acid resin, polyaspartic acid resin, and dispersant at a rotation speed of 1000 rpm to 2500 rpm for 10 to 30 minutes; A2: Add the filler and color paste, and stir at a rotation speed of 1000 rpm to 2500 rpm for 10 to 30 minutes; A3: Add the defoamer and anti-wear agent, and stir at a rotation speed of 700 rpm to 1500 rpm for 10 to 30 minutes to obtain Component A; Preparation of Component B: B1: Stir the hexamethylene diisocyanate trimer, isocyanate prepolymer, isocyanate, and dispersant at a rotation speed of 1000 rpm to 2500 rpm for 10 to 30 minutes; B2: Add the filler and stir at a rotation speed of 1000 rpm to 2500 rpm for 10 to 30 minutes; B3: Add the defoamer and stir at a rotation speed of 700 rpm to 1500 rpm for 10 to 30 minutes to obtain Component B.

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