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 seam beautifying agent with high tensile strength and bonding strength, comprising component A and component B, which are measured 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 defoaming agent, 0.1-0.8 parts of dispersant, 1-4 parts of anti-wear agent;

[0011] The modified polyaspartic acid resin is prepared from 6 to 40 parts of epoxy resin, 60 to 100 parts of polyaspartic acid resin, and 0 to 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 to 80 parts of polyol, 20 to 80 parts of isocyanate, 0 to 20 parts of plasticizer, and 0.1 to 1.0 parts of catalyst;

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

[0016] The present invention modifies polyaspartic acid resin by using epoxy resin, and then prepares a novel modified aspartic acid polyurea seam beautifying agent by reacting the modified polyaspartic acid resin with a curing agent component. The modified polyurea seam beautifying agent prepared by the preparation method of 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.

[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. to 110° C. for 5 h to 24 h.

[0018] The reaction example of the modified polyaspartic acid resin is shown below:

[0019]

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

[0021] Furthermore, 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, and HBE7210.

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

[0023] Furthermore, 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. to 120° C. for 5 h to 24 h to obtain the isocyanate prepolymer.

[0024] An example of the reaction of the isocyanate prepolymer is shown below:

[0025]

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

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

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

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

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

[0031] Furthermore, the defoaming agent is a phosphate ester or organosilicon compound defoaming agent.

[0032] Furthermore, 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 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.

[0047] Embodiment 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 parts of organic bismuth catalyst were added into a reactor, 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 parts of organic bismuth catalyst were added into a reactor, 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 parts of an organic bismuth catalyst were added into a reaction kettle, and reacted at a reaction temperature of 90° C. for 10 hours to obtain an isocyanate prepolymer A.

[0054] The preparation of a modified polyurea seam sealant with high tensile strength and bonding strength includes component A and component B in 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 parts of BYK110 dispersant were stirred at a speed of 1500 rpm for 15 minutes;

[0057] A2: Add 8 parts of fumed silica and 4 parts of titanium white slurry, and stir at 2000 rpm for 20 minutes;

[0058] A3: Add 0.1 parts of BYK 012 defoamer and 2 parts of glass powder, and stir at 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 parts of BYK110 dispersant were stirred at a rotation speed of 1500 rpm for 15 minutes;

[0061] 2) adding 6 parts of fumed silica and stirring at 2000 rpm for 20 minutes;

[0062] 3) Add 0.1 parts of BYK 012 defoamer and stir at 1500 rpm for 15 minutes to obtain component B.

[0063] Embodiment 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 parts of organic bismuth catalyst were added into a reactor and reacted at a reaction temperature of 70° C. for 12 hours to obtain modified polyaspartic acid resin C.

[0066] Preparation of isocyanate prepolymer B:

[0067] 63 parts of C2010 polyether polyol, 37 parts of isophorone diisocyanate and 0.1 parts of organic bismuth catalyst were added into a reaction kettle by weight, and reacted at a reaction temperature of 90° C. for 10 hours to obtain isocyanate prepolymer B.

[0068] The preparation of a modified polyurea seam sealant with high tensile strength and bonding strength includes component A and component B in 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 parts of BYK110 dispersant were stirred at a speed of 1500 rpm for 15 minutes;

[0071] 2) Add 8 parts of fumed silica and 4 parts of titanium white slurry, and stir at 2000 rpm for 20 minutes;

[0072] 3) Add 0.1 parts of BYK 012 defoamer and 2 parts of glass powder, and stir at 1500 rpm for 15 minutes to obtain component A.

[0073] Preparation of component B:

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

[0075] 2) adding 6 parts of fumed silica and stirring at 2000 rpm for 20 minutes;

[0076] 3) Add 0.1 parts of BYK 012 defoamer and stir at 1500 rpm for 15 minutes to obtain component B.

[0077] Embodiment 3:

[0078] Preparation of modified polyaspartic acid resin C:

[0079] The same as Example 2, no further details are given here.

[0080] Preparation of modified polyaspartic acid resin D:

[0081] By weight, 100 parts of W520 polyaspartic acid resin (Yantai Wanshun New Materials Co., Ltd.), 12.5 parts of PNE177M80 epoxy resin, and 0.1 parts of organic bismuth catalyst were added into a reactor and reacted at a reaction temperature of 80° C. for 15 hours to obtain modified polyaspartic acid resin D.

[0082] Preparation of isocyanate prepolymer C:

[0083] 71 parts of C2020 polyether polyol, 29 parts of isophorone diisocyanate and 0.1 parts of organic bismuth catalyst were added into a reaction kettle by weight, and reacted at a reaction temperature of 90° C. for 15 hours to obtain isocyanate prepolymer C.

[0084] The preparation of a modified polyurea seam sealant with high tensile strength and bonding strength includes component A and component B in a mass ratio of 1:1:

[0085] Preparation of component A:

[0086] 1) By weight, 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 parts of BYK110 dispersant were stirred at a speed of 1500 rpm for 15 minutes;

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

[0088] 3) Add 0.1 parts of BYK 012 defoamer and 2 parts of glass powder, and stir at 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 parts of BYK110 dispersant were stirred at a speed of 1500 rpm for 15 minutes;

[0091] 2) adding 6 parts of fumed silica and stirring at 2000 rpm for 20 minutes;

[0092] 3) Add 0.1 parts of BYK 012 defoamer and stir at 1500 rpm for 15 minutes to obtain component B.

[0093] Comparative Example 1:

[0094] Traditional seam beautifying agent: polyurea seam beautifying agent from Weifang Ancai New Materials Co., Ltd., which has good market sales and effects.

[0095] Performance Test:

[0096] 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".

[0097] 2. 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.

[0098] 3. 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.

[0099] 4. 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.

[0100] 5. 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".

[0101] 6. 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".

[0102] 7. 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".

[0103] 8. Bond strength test: The above-mentioned Examples 1 to 3 and the traditional caulking agent were subjected to a bond strength test, and 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 to 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 6mg Scratch resistance No scratches No scratches No scratches Slightly scratched Contractility No shrinkage No shrinkage No shrinkage Slightly shrink Tensile strength, MPa 22 24 26 15 Elongation at break, % 43 36 35 20 Shore Hardness 71 72 70 71 Bond strength, Mpa 18 22 21 9

[0107] It can be seen from the test data in Table 1 that the polyurea seam beautifying agent prepared by using the homemade modified polyaspartic acid resin and modified isocyanate prepolymer as raw materials in the present invention has the characteristics of high tensile strength and high bonding strength, and other performance indicators have no obvious disadvantages compared with the traditional seam beautifying agent in Comparative Example 1. The performance of the modified polyurea seam beautifying agent described in 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 seam beautifying agent.

[0108] 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. A modified polyurea seam beautifying agent with high tensile strength and bonding strength, characterized in that: Including 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 parts of defoaming agent, 0.1-0.8 parts of dispersant, 1-4 parts of anti-wear agent; The modified polyaspartic acid resin is prepared from 6 to 40 parts of epoxy resin, 60 to 100 parts of polyaspartic acid resin, and 0 to 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 parts of defoamer, 0.1-0.8 parts of dispersant; The isocyanate prepolymer is prepared from 20 to 80 parts of polyol, 20 to 80 parts of isocyanate, 0 to 20 parts of plasticizer, and 0.1 to 1.0 parts of catalyst; The mass ratio of the component A to the component B is 1:1.0-1.

2.

2. The modified polyurea seam beautifying agent with high tensile strength and bonding strength according to claim 1, characterized in that: The preparation method of the modified polyaspartic acid resin comprises the following steps: adding epoxy resin, polyaspartic acid resin and a catalyst into a reaction kettle, and reacting the mixture at a reaction temperature of 60° C. to 110° C. for 5 h to 24 h.

3. The modified polyurea seam beautifying agent with high tensile strength and bonding strength according to claim 1, characterized in that: The preparation method of the isocyanate prepolymer is as follows: polyol, isocyanate, plasticizer and catalyst are added into a reaction kettle, and the reaction is carried out at a reaction temperature of 80° C. to 120° C. for 5 h to 24 h to obtain the isocyanate prepolymer.

4. The modified polyurea seam beautifying 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, and HBE7210.

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

6. The modified polyurea seam beautifying 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 and polycarbonate polyol; the isocyanate is one or more of isophorone diisocyanate, 2,2,4-trimethylhexane diisocyanate, dicyclohexylmethane diisocyanate, naphthalene-1,5-diisocyanate and hexamethylene diisocyanate.

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

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

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

10. A method for preparing the modified polyurea seam beautifying agent with high tensile strength and bonding strength as claimed in any one of claims 1 to 9, characterized in that: The steps include: Preparation of component A: 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; A2: Add filler and color paste, and stir at 1000rpm-2500rpm for 10-30 minutes; 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; Preparation of component B: B1: Stir hexamethylene diisocyanate trimer, isocyanate prepolymer, isocyanate and dispersant at a speed of 1000 rpm to 2500 rpm for 10 to 30 minutes; B2: Add filler and stir at 1000 rpm to 2500 rpm for 10 to 30 minutes; 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.

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