High-cohesiveness anti-aging tile adhesive and preparation method thereof

Abstract

The invention relates to the technical field of building materials, in particular to high-cohesiveness anti-aging tile glue and a preparation method thereof. The high-cohesiveness anti-aging ceramic tile adhesive is prepared from the following components in parts by weight: 10 to 50 parts of epoxy functional siloxane resin, 40 to 60 parts of cement, 5 to 20 parts of hardening agent, 5 to 10 parts of thickening agent, 1 to 5 parts of antioxidant and 20 to 30 parts of filler, the structural formula of the epoxy functional siloxane resin is as follows: # imgabs0 #. The ceramic tile adhesive has excellent cohesiveness and ageing resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of building materials, and particularly relates to a high-bonding anti-aging tile adhesive and a preparation method thereof. Background Art

[0002] Traditionally, the bonding between tiles and walls is mainly achieved through cement. However, the above method is prone to problems such as tile hollowing and easy detachment. With the development of technology, tile adhesives have gradually replaced cement and become new materials for modern decoration. Tile adhesives are mainly used for pasting decorative materials such as tiles, facing bricks, and floor tiles, and are widely applicable to the decorative finishing places of buildings such as interior and exterior walls, floors, bathrooms, and kitchens.

[0003] Currently, a variety of tile adhesives have emerged on the market. For example, Chinese Patent CN116217179A, a high-bonding anti-aging tile adhesive and a preparation method thereof, discloses changing the bonding strength and anti-aging performance of tile adhesives by adding an organosilicon - higher fatty acid composite water repellent. Chinese Patent CN112390590A, a high-bonding gelling material and a high-strength permeable cement concrete material, discloses improving the performance of tile adhesives by microsilica, basalt fiber, and reinforcing agents, etc. However, it is found in practice that the above tile adhesives either have poor bonding strength or poor anti-aging effect. Based on this, the present invention aims to provide a tile adhesive with both high bonding strength and good anti-aging performance. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, one of the purposes of the present invention is to provide a high-bonding anti-aging tile adhesive with excellent bonding property and anti-aging property.

[0005] Another purpose of the present invention is to provide a preparation method of a high-bonding anti-aging tile adhesive with a simple process.

[0006] The purpose one of the present invention is achieved by adopting the following technical solution:

[0007] A high-bonding anti-aging tile adhesive, in parts by weight, comprises the following components: 10 - 50 parts of epoxy-functionalized siloxane resin, 40 - 60 parts of cement, 5 - 20 parts of hardener, 5 - 10 parts of thickener, 1 - 5 parts of antioxidant, and 20 - 30 parts of filler; the structural formula of the epoxy-functionalized siloxane resin is as follows:

[0008]

[0009] Further, the preparation process of the epoxy-functionalized siloxane resin is as follows:

[0010] (1) Mix polycarbonate diol, toluene-2,4-diisocyanate, and dibutyltin dilaurate, and heat them for reaction under an inert gas atmosphere for 2 - 3 h. Then add 4,4'-diaminodiphenyl disulfide and toluene-2,4-diisocyanate and continue the reaction for 2 - 3 h. After the reaction is completed, add acetone for dilution to obtain the reaction solution of intermediate 1; add the acetone solution of γ-aminopropyltriethoxysilane to the above reaction solution of intermediate 1 and stir for reaction. After the reaction is completed, obtain the reaction solution of intermediate 2;

[0011] (2) Add sodium bicarbonate solution to the reaction solution of intermediate 2 and stir for reaction. After the reaction is completed, dialyze and freeze-dry the reaction solution to obtain intermediate 3;

[0012] (3) Add the intermediate 3 obtained in step (2) to acetone, then add epichlorohydrin and sodium hydroxide for reaction. After the reaction is completed, purify the reaction solution to obtain the epoxy-functionalized silicone resin.

[0013] Furthermore, the molar ratio of dibutyltin dilaurate, polycarbonate diol, 4,4'-diaminodiphenyl disulfide, and γ-aminopropyltriethoxysilane in step (1) is (0.03 - 0.1):(8 - 12):(8 - 12):5; the molar ratio of the total amount of toluene-2,4-diisocyanate added twice in step (1) to polycarbonate diol is (8 - 12):(25 - 38); the concentration of γ-aminopropyltriethoxysilane in the acetone solution of γ-aminopropyltriethoxysilane is 0.25 mmol / L.

[0014] Furthermore, the temperature of the heating reaction in step (1) is 85 - 95 °C, and the heating reaction time is 3 - 5 h; the stirring reaction time is 0.5 - 1.5 h.

[0015] Furthermore, the volume ratio of the reaction solution of intermediate 2 to the sodium bicarbonate solution in step (2) is 1:(5 - 10); the concentration of the sodium bicarbonate solution is 0.1 mol / L; the stirring reaction time is 22 - 26 h.

[0016] Furthermore, the dosage ratio of intermediate 3, epichlorohydrin, and sodium hydroxide in step (3) is 1:(0.5 - 1.5):(0.05 - 0.15); the reaction temperature is 55 - 65 °C, and the reaction time is 3.5 - 4.5 h.

[0017] Furthermore, the antioxidant is antioxidant GA-80, the hardener is triethylenetetramine or diethylenetriamine, and the thickener is hydroxypropyl methylcellulose or hydroxyethyl methylcellulose.

[0018] Further, the filler is compounded from basalt fiber and wollastonite fiber in a weight ratio of 1:(0.5 - 0.8); the cement is Portland cement.

[0019] The second object of the present invention is achieved by the following technical solution:

[0020] The preparation method of the above high - adhesion anti - aging tile adhesive includes the following steps:

[0021] Mix the components evenly according to the said weight parts and stir, and the high - adhesion anti - aging tile adhesive is obtained after discharging.

[0022] Further, the stirring speed is 200 - 250 rpm, and the stirring time is 25 - 35 min.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] The tile adhesive of the present invention contains epoxy - functionalized siloxane resin, antioxidant, hardener and other components. Among them, the epoxy - functionalized siloxane resin has the toughness of polyurethane, the inorganic adhesion of siloxane and the high reactivity of epoxy resin. On the one hand, it contains carbonyl functional groups that can form hydrogen bonds with antioxidants, thus playing an anti - aging role; on the other hand, when used in combination with hardeners, it can form a high - crosslinking - density network, thereby significantly improving the bonding strength of the tile adhesive. Specific Embodiments

[0025] The following combines specific embodiments to further describe the present invention. It should be noted that, on the premise of no conflict, the following described embodiments or technical features can be combined arbitrarily to form new embodiments. The specific conditions not specified in the embodiments are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, unless otherwise specified, are all conventional products obtained through commercial channels.

[0026] Embodiments

[0027] Embodiment 1

[0028] Embodiment 1 provides a high - adhesion anti - aging tile adhesive. By weight, the high - adhesion anti - aging tile adhesive consists of the following components: 20 parts of epoxy - functionalized siloxane resin, 50 parts of P.042.5 ordinary Portland cement, 12 parts of triethylenetetramine, 7 parts of hydroxypropyl methylcellulose, 2 parts of antioxidant GA - 80 (CAS No.: 90498 - 90 - 1), 25 parts of filler (compounded from basalt fiber and wollastonite fiber in a weight ratio of 1:0.6); the structural formula of the epoxy - functionalized siloxane resin is as follows:

[0029]

[0030] The specific preparation process of the above epoxy-functionalized silicone resin is as follows:

[0031]

[0032] (1) Add polycarbonate diol (10 mmol) and toluene-2,4-diisocyanate (21 mmol) into a flask, then add dibutyltin dilaurate (0.05 mmol), and react at 90 °C under nitrogen protection for 2 h. Then add 4,4'-diaminodiphenyl disulfide (10 mmol) and toluene-2,4-diisocyanate (11 mmol), and continue to react for 2 h. After the reaction is completed, add 100 mL of acetone for dilution to obtain the reaction solution of intermediate 1. Dropwise add 20 mL of an acetone solution of γ-aminopropyltriethoxysilane with a concentration of 0.25 mmol / L to the above reaction solution at 90 °C and react for 1 h. After the reaction is completed, cool down to room temperature to obtain the reaction solution of intermediate 2;

[0033] (2) With the volume ratio of the reaction solution of intermediate 2 to the sodium bicarbonate solution being 1:8, add a 0.1 mol / L sodium bicarbonate solution to the reaction solution of intermediate 2 obtained in step (1) and stir for 24 h. After the reaction is completed, dialyze with a dialysis membrane with a cut-off molecular weight of 1000 Da for 24 h, and freeze-dry to obtain intermediate 3;

[0034] (3) Add the intermediate 3 (5 g) in step (2) to 150 mL of acetone, then add epichlorohydrin (5 g) and sodium hydroxide (0.5 g), and react at 60 °C for 4 h. After the reaction is completed, add water to the reaction solution, separate the organic layer, and dry it with anhydrous magnesium sulfate to obtain the epoxy-functionalized silicone resin.

[0035] The NMR and GPC results of the epoxy-functionalized silicone resin are as follows:

[0036] 1 HNMR (400 MHz, d6-DMSO) δ = 0.58 (t, 4H), 1.53 (m, 4H), 2.21 (m, 9H), 2.37 - 2.62 (m, 18H), 3.40 (t, 4H), 3.79 m(, 6H), 4.05 (m, 6H), 6.01 (s, 2H), 6.97 (s, 4H), 7.34 - 7.38 (m, 6H), 7.74 - 7.80 (t, 7H), 8.10 (d, 4H), 8.28 (s, 1H), 8.77 (s, 2H), 8.92 (s, 1H), 9.29 (s, 2H), 9.88 (s, 2H); GPC: Mn = 5180 g / mol.

[0037] Example 1 also provides a preparation method of the above high-adhesion anti-aging tile adhesive, which is as follows:

[0038] According to the stated parts by weight, mix all components evenly, stir at a speed of 220 rpm for 30 min, and the high-adhesion anti-aging tile adhesive can be obtained after discharging.

[0039] Example 2

[0040] Example 2 provides a high-adhesion anti-aging tile adhesive. In terms of parts by weight, the high-adhesion anti-aging tile adhesive is composed of the following components: 10 parts of epoxy-functionalized siloxane resin, 40 parts of P.O 42.5 ordinary portland cement, 5 parts of diethylenetriamine, 5 parts of hydroxyethyl methyl cellulose, 1 part of antioxidant GA-80 (CAS No.: 90498-90-1), and 20 parts of filler (compounded by basalt fiber and wollastonite fiber according to a weight ratio of 1:0.5); the structural formula of the above epoxy-functionalized siloxane resin is the same as that in Example 1.

[0041] The specific preparation process of the above epoxy-functionalized siloxane resin is as follows:

[0042] (1) Add polycarbonate diol (8 mmol) and toluene-2,4-diisocyanate (16 mmol) into a flask, then add dibutyltin dilaurate (0.03 mmol), react at 85 °C under nitrogen protection for 2 h, then add 4,4'-diaminodiphenyl disulfide (8 mmol) and toluene-2,4-diisocyanate (9 mmol) and continue to react for 3 h. After the reaction is completed, add 100 mL of acetone for dilution to obtain the reaction solution of intermediate 1; dropwise add 20 mL of an acetone solution of 0.25 mmol / L γ-aminopropyltriethoxysilane to the above reaction solution at 85 °C and react for 0.5 h. After the reaction is completed, cool down to room temperature to obtain the reaction solution of intermediate 2;

[0043] (2) With the volume ratio of the reaction solution of intermediate 2 to the sodium bicarbonate solution being 1:5, add 0.1 mol / L sodium bicarbonate solution to the reaction solution of intermediate 2 obtained in step (1) and stir for 22 h. After the reaction is completed, dialyze with a dialysis membrane with a cut-off molecular weight of 1000 Da for 24 h, and freeze-dry to obtain intermediate 3;

[0044] (3) Add the intermediate 3 (5 g) in step (2) to 120 mL of acetone, then add epichlorohydrin (2.5 g) and sodium hydroxide (0.25 g), react at 55 °C for 4.5 h. After the reaction is completed, add water to the reaction solution, separate the organic layer, and dry with anhydrous magnesium sulfate to obtain the epoxy-functionalized siloxane resin; the GPC of the obtained epoxy-functionalized siloxane resin: Mn = 5318 g / mol.

[0045] Example 2 also provides a method for preparing the above high-adhesion anti-aging tile adhesive, which is as follows:

[0046] Mix all components evenly according to the specified weight parts, stir at a speed of 200 rpm for 35 min, and the high-adhesion anti-aging tile adhesive can be obtained after discharging.

[0047] Example 3

[0048] Example 3 provides a high-adhesion anti-aging tile adhesive. Calculated by weight parts, the high-adhesion anti-aging tile adhesive is composed of the following components: 50 parts of epoxy-functionalized siloxane resin, 60 parts of P.O 42.5 ordinary Portland cement, 20 parts of triethylenetetramine, 10 parts of hydroxypropyl methylcellulose, 5 parts of antioxidant GA-80 (CAS No.: 90498-90-1), 30 parts of filler (compounded by basalt fiber and wollastonite fiber according to a weight part ratio of 1:0.8); the structural formula of the above epoxy-functionalized siloxane resin is the same as that in Example 1.

[0049] The specific preparation process of the above epoxy-functionalized siloxane resin is as follows:

[0050] (1) Add polycarbonate diol (12 mmol) and toluene-2,4-diisocyanate (25 mmol) into a flask, then add dibutyltin dilaurate (0.1 mmol), react at 95 °C under nitrogen protection for 2 h, then add 4,4'-diaminodiphenyl disulfide (12 mmol) and toluene-2,4-diisocyanate (13 mmol) and continue to react for 3 h. After the reaction is completed, add 100 mL of acetone for dilution to obtain the reaction solution of intermediate 1; dropwise add 20 mL of a 0.25 mmol / L acetone solution of γ-aminopropyltriethoxysilane to the above reaction solution at 95 °C and react for 1.5 h. After the reaction is completed, cool down to room temperature to obtain the reaction solution of intermediate 2;

[0051] (2) With the volume ratio of the reaction solution of intermediate 2 to the sodium bicarbonate solution being 1:10, add 0.1 mol / L sodium bicarbonate solution to the reaction solution of intermediate 2 obtained in step (1) and stir for 26 h. After the reaction is completed, dialyze for 24 h using a dialysis membrane with a cut-off molecular weight of 1000 Da, and freeze-dry to obtain intermediate 3;

[0052] (3) Add the intermediate 3 (5 g) in step (2) to 160 mL of acetone, then add epichlorohydrin (6.5 g) and sodium hydroxide (0.65 g), react at 65 °C for 3.5 h. After the reaction is completed, add water to the reaction solution, separate the organic layer, and dry with anhydrous magnesium sulfate to obtain the epoxy-functionalized siloxane resin; the GPC of the obtained epoxy-functionalized siloxane resin: Mn = 5230 g / mol.

[0053] Example 3 also provides a method for preparing the above high-adhesion anti-aging tile adhesive, which is specifically as follows:

[0054] According to the above weight parts, mix each component evenly, stir at a speed of 250 rpm for 25 min, and the high-adhesion anti-aging tile adhesive can be obtained after discharging.

[0055] Comparative Example

[0056] Comparative Example 1

[0057] The difference between Comparative Example 1 and Example 1 is that epoxy resin is used to replace epoxy-functionalized siloxane resin, and the rest is the same as Example 1.

[0058] Comparative Example 2

[0059] The difference between Comparative Example 2 and Example 1 is that the antioxidant is omitted, and the rest is the same as Example 1.

[0060] Experimental Example

[0061] Refer to the detection method in JC / T547-2017 "Ceramic Wall and Floor Tile Adhesive" to detect the performance of the tile adhesives obtained in Examples 1-3 and Comparative Examples 1-2. The results are shown in Table 1.

[0062] Table 1

[0063]

[0064]

[0065] As can be seen from Table 1, the tile adhesives obtained in Examples 1-3 have excellent bonding strength and anti-aging performance. Compared with Example 1, in Comparative Example 1, epoxy-functionalized siloxane resin was replaced by epoxy resin, and in Comparative Example 2, the antioxidant was omitted. By comparing the data of Example 1 with those of Comparative Examples 1-2, it can be seen that the combination of epoxy-functionalized siloxane resin and antioxidant in the present invention can significantly improve the bonding strength and anti-aging property of the tile adhesive. The reason is that the antioxidant can form hydrogen bonds with the carbonyl group in the epoxy-functionalized siloxane resin, thereby improving the anti-aging effect; after the epoxy-functionalized siloxane resin is used in combination with the hardener, a high cross-linking density network is formed, significantly improving the bonding strength of the tile adhesive.

[0066] The above embodiments are only the preferred embodiments of the present invention, and the scope of protection of the present invention cannot be limited thereby. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of protection required by the present invention.

Claims

1. A high-adhesion and anti-aging tile adhesive, characterized in that, By weight parts, it includes the following components: 10 - 50 parts of epoxy-functionalized silicone resin, 40 - 60 parts of cement, 5 - 20 parts of hardener, 5 - 10 parts of thickener, 1 - 5 parts of antioxidant, and 20 - 30 parts of filler; the structural formula of the epoxy-functionalized silicone resin is as follows:

2. The high-adhesion anti-aging tile adhesive according to claim 1, characterized in that, The preparation process of the epoxy-functionalized silicone resin is as follows: (1) Mix polycarbonate diol, toluene-2,4-diisocyanate, and dibutyltin dilaurate and heat and react for 2 - 3 h under an inert gas atmosphere, then add 4,4'-diaminodiphenyl disulfide and toluene-2,4-diisocyanate and continue to react for 2 - 3 h. After the reaction is completed, add acetone for dilution to obtain the reaction solution of intermediate 1; add the acetone solution of γ-aminopropyltriethoxysilane to the above reaction solution of intermediate 1 and stir and react. After the reaction is completed, obtain the reaction solution of intermediate 2; (2) Add sodium bicarbonate solution to the reaction solution of intermediate 2 and stir and react. After the reaction is completed, the reaction solution is dialyzed and freeze-dried to obtain intermediate 3; (3) Add the intermediate 3 in step (2) to acetone, then add epichlorohydrin and sodium hydroxide for reaction. After the reaction is completed, the reaction solution is purified to obtain the epoxy-functionalized silicone resin.

3. The highly adhesive anti-aging tile adhesive according to claim 2, wherein In step (1), the molar ratio of dibutyltin dilaurate, polycarbonate diol, 4,4'-diaminodiphenyl disulfide, and γ-aminopropyltriethoxysilane is (0.03 - 0.1):(8 - 12):(8 - 12):5; the molar ratio of the total amount of toluene-2,4-diisocyanate added twice in step (1) to polycarbonate diol is (8 - 12):(25 - 38); the concentration of γ-aminopropyltriethoxysilane in the acetone solution of γ-aminopropyltriethoxysilane is 0.25 mmol / L.

4. The high-bonding anti-aging tile adhesive according to claim 2, wherein In step (1), the temperature of the heating reaction is 85 - 95 °C, and the time of the heating reaction is 3 - 5 h; the time of the stirring reaction is 0.5 - 1.5 h.

5. The high-adhesion anti-aging tile adhesive according to claim 2, characterized in that, In step (2), the volume ratio of the reaction solution of intermediate 2 to the sodium bicarbonate solution is 1:(5 - 10); the concentration of the sodium bicarbonate solution is 0.1 mol / L; the time of the stirring reaction is 22 - 26 h.

6. The high-bonding anti-aging tile adhesive according to claim 2, characterized in that, In step (3), the dosage ratio of intermediate 3, epichlorohydrin, and sodium hydroxide is 1:(0.5 - 1.5):(0.05 - 0.15); the temperature of the reaction is 55 - 65 °C, and the time of the reaction is 3.5 - 4.5 h.

7. The high-adhesion anti-aging tile adhesive according to claim 1, wherein The antioxidant is antioxidant GA-80, the hardener is triethylenetetramine or diethylenetriamine, and the thickener is hydroxypropyl methylcellulose or hydroxyethyl methylcellulose.

8. The high-adhesion anti-aging tile adhesive according to claim 1, wherein The filler is compounded by basalt fiber and wollastonite fiber according to the weight parts of 1:(0.5 - 0.8); the cement is Portland cement.

9. The preparation method of the highly adhesive anti-aging tile adhesive according to any one of claims 1-8, characterized in that, It includes the following steps: According to the above weight parts, mix each component evenly and stir. After discharging, the high-adhesion anti-aging tile adhesive is obtained.

10. The preparation method of the highly adhesive anti-aging tile adhesive according to claim 9, characterized in that, The speed of the stirring is 200 - 250 rpm, and the time of the stirring is 25 - 35 min.

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