High-adhesion anti-aging ceramic tile adhesive and preparation method thereof

Abstract

The application relates to the technical field of building materials, in particular to high-adhesion anti-aging ceramic tile glue and a preparation method thereof. The high-adhesion anti-aging ceramic tile glue comprises the following components in parts by weight: 10-50 parts of epoxy-functionalized siloxane resin, 40-60 parts of cement, 5-20 parts of hardening agent, 5-10 parts of thickening agent, 1-5 parts of antioxidant and 20-30 parts of filler; the structural formula of the epoxy-functionalized siloxane resin is shown in the description. The ceramic tile glue has excellent adhesion and anti-aging property.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building materials, and in particular to a high-adhesion anti-aging ceramic tile glue and a preparation method thereof. BACKGROUND

[0002] Traditional ceramic tiles and wall surfaces are mainly bonded by cement, but the above-mentioned method is prone to cause problems such as ceramic tile hollowing and easy falling off. With the development of science and technology, ceramic tile glue gradually replaces cement and becomes a new material for modern decoration. Ceramic tile glue is mainly used for sticking decorative materials such as ceramic tiles, face bricks and floor tiles, and is widely used in the decoration of interior and exterior walls, floors, bathrooms and kitchens.

[0003] At present, various ceramic tile glues have appeared on the market, such as a high-adhesion anti-aging ceramic tile glue and a preparation method thereof disclosed in Chinese patent CN116217179A, which discloses changing the bonding strength and anti-aging performance of ceramic tile glue by adding silicone-higher fatty acid composite hydrophobic agent. Chinese patent CN112390590A discloses a high-adhesion cementitious material and a high-strength water-permeable cement concrete material, which improves the performance of ceramic tile glue by using micro-silica powder, basalt fiber and reinforcing agent. However, it is found in practice that the above-mentioned ceramic tile glue has problems of poor bonding strength or poor aging resistance. Therefore, the present application aims to provide a ceramic tile glue with high bonding strength and good aging resistance. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, one of the purposes of the present application is to provide a high-adhesion anti-aging ceramic tile glue with excellent bonding and anti-aging properties.

[0005] The second purpose of the present application is to provide a preparation method of a high-adhesion anti-aging ceramic tile glue, which is simple in process.

[0006] One of the purposes of the present application is achieved by adopting the following technical solutions:

[0007] A high-adhesion anti-aging ceramic tile glue, comprising the following components in parts by weight: epoxy-functionalized siloxane resin 10-50 parts, cement 40-60 parts, hardening agent 5-20 parts, thickening agent 5-10 parts, antioxidant 1-5 parts, and filler 20-30 parts; 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) mixing polycarbonate diol, toluene-2, 4-diisocyanate and dibutyl tin dilaurate and heating the mixture under inert gas atmosphere for 2-3h, then adding 4, 4'-diamino diphenyl disulfide and toluene-2, 4-diisocyanate and continuing the reaction for 2-3h, after the reaction is completed, adding acetone to dilute the reaction solution to obtain intermediate 1; adding the acetone solution of γ-aminopropyl triethoxysilane to the reaction solution of intermediate 1 and stirring to react, after the reaction is completed, obtaining the reaction solution of intermediate 2;

[0011] (2) adding sodium bicarbonate solution to the reaction solution of intermediate 2 and stirring to react, after the reaction is completed, the reaction solution is dialyzed and freeze-dried to obtain intermediate 3;

[0012] (3) adding intermediate 3 of step (2) to acetone, then adding epichlorohydrin and sodium hydroxide to react, after the reaction is completed, the reaction solution is purified to obtain the epoxy functionalized siloxane resin.

[0013] Further, in step (1), the molar ratio of dibutyl tin dilaurate, polycarbonate diol, 4, 4'-diamino diphenyl disulfide and γ-aminopropyl triethoxysilane is (0.03-0.1) : (8-12) : (8-12) : 5; the total amount of toluene-2, 4-diisocyanate added twice in step (1) and the polycarbonate diol have a molar ratio of (8-12) : (25-38); the concentration of γ-aminopropyl triethoxysilane in the acetone solution of γ-aminopropyl triethoxysilane is 0.25 mmol / L.

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

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

[0016] Further, in step (3), the amount 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℃, and the time of the reaction is 3.5-4.5h.

[0017] Further, the antioxidant is antioxidant GA-80, the hardener is triethylenetetramine or diethylenetriamine, and the thickening agent is hydroxypropyl methylcellulose or hydroxyethyl methylcellulose.

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

[0019] The second purpose of the present application is achieved by the following technical scheme:

[0020] The preparation method of the high-adhesion anti-aging ceramic tile glue comprises the following steps:

[0021] According to the weight fraction, the components are mixed uniformly and stirred, and the high-adhesion anti-aging ceramic tile glue 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 present application has the following advantages:

[0024] The ceramic tile glue contains epoxy functionalized siloxane resin and antioxidant, hardening agent and other components. The epoxy functionalized siloxane resin has the properties of polyurethane toughness, siloxane inorganic adhesion and epoxy resin high reactivity, etc. On the one hand, it contains carbonyl functional group which can form hydrogen bond with antioxidant, thereby playing an anti-aging role; on the other hand, it can form a high crosslinking density network after being used with hardening agent, thereby significantly improving the bonding strength of the ceramic tile glue. DETAILED DESCRIPTION

[0025] The present application will be further described below in conjunction with specific embodiments. It should be noted that the embodiments described below or the technical features thereof can be combined in any manner to form new embodiments without conflict. The specific conditions not mentioned in the embodiments are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, such as those not specifically mentioned, are conventional products obtained through commercial channels.

[0026] EMBODIMENT

[0027] EMBODIMENT 1

[0028] Embodiment 1 provides a high-adhesion anti-aging ceramic tile glue, which is composed of the following components in weight fraction: epoxy functionalized siloxane resin 20 parts, P.042.5 ordinary Portland cement 50 parts, triethylenetetramine 12 parts, hydroxypropyl methylcellulose 7 parts, antioxidant GA-80 (CAS No. 90498-90-1) 2 parts, filler 25 parts (compounded by 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-mentioned epoxy functionalized siloxane resin is as follows:

[0031]

[0032] (1) Polycarbonate diol (10 mmol), toluene-2, 4-diisocyanate (21 mmol) were added into a flask, then dibutyltin dilaurate (0.05 mmol) was added, and the reaction was carried out at 90°C under nitrogen protection for 2h, then 4, 4'-diamino diphenyl disulfide (10 mmol) and toluene-2, 4-diisocyanate (11 mmol) were added, and the reaction was continued for 2h, then 100 mL of acetone was added for dilution to obtain the reaction solution of intermediate 1; 20 mL of 0.25 mmol / L γ-aminopropyl triethoxysilane acetone solution was added dropwise to the above-mentioned reaction solution at 90°C and reacted for 1h, and then the reaction was cooled to room temperature to obtain the reaction solution of intermediate 2;

[0033] (2) The reaction solution of intermediate 2 obtained in step (1) was added with 0.1 mol / L sodium bicarbonate solution in a volume ratio of 1:8, and the mixture was stirred for 24h, then dialysis was carried out using a dialysis membrane with a molecular weight cut-off of 1000 Da for 24h, and then freeze-drying was carried out to obtain intermediate 3;

[0034] (3) Intermediate 3 (5g) of step (2) was added into 150 mL of acetone, then epichlorohydrin (5g) and sodium hydroxide (0.5g) were added, and the mixture was reacted at 60°C for 4h, then water was added to the reaction solution, the organic layer was separated, and anhydrous magnesium sulfate was used for drying to obtain the epoxy functionalized siloxane resin.

[0035] The results of nuclear magnetic resonance and GPC of the epoxy functionalized siloxane resin are as follows:

[0036] 1 HNMR (400MHz, 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), 3.79m (, 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] The embodiment 1 also provides a preparation method of the high-adhesion anti-aging ceramic tile glue, and the preparation method specifically comprises the following steps:

[0038] According to the weight parts, the components are uniformly mixed, stirred at a speed of 220 rpm for 30 min, and the high-adhesion anti-aging ceramic tile glue is obtained after discharging.

[0039] Embodiment 2

[0040] The embodiment 2 provides a high-adhesion anti-aging ceramic tile glue, and the high-adhesion anti-aging ceramic tile glue is composed of the following components in parts by weight: 10 parts of epoxy functionalized siloxane resin, 40 parts of P.042.5 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 fillers (which are compounded by basalt fibers and wollastonite fibers at a weight ratio of 1:0.5); and the structural formula of the epoxy functionalized siloxane resin is the same as that in the embodiment 1.

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

[0042] (1) polycarbonate diol (8 mmol), toluene-2,4-diisocyanate (16 mmol) are added into a flask, then dibutyltin dilaurate (0.03 mmol) is added, and reaction is carried out at 85°C under nitrogen protection for 2h, then 4,4'-diamino diphenyl disulfide (8 mmol), toluene-2,4-diisocyanate (9 mmol) are further added, and reaction is continued for 3h, after reaction is completed, 100 mL of acetone is added for dilution, and a reaction solution of intermediate 1 is obtained; 20 mL of 0.25 mmol / L γ-aminopropyl triethoxysilane acetone solution is added dropwise to the reaction solution under the condition of 85°C for 0.5h, after reaction is completed, the temperature is lowered to room temperature, and a reaction solution of intermediate 2 is obtained;

[0043] (2) with the volume ratio of the reaction solution of intermediate 2 to sodium bicarbonate solution being 1:5, 0.1 mol / L sodium bicarbonate solution is added to the reaction solution of intermediate 2 obtained in step (1) for stirring for 22h, after reaction is completed, dialysis is carried out for 24h by using a dialysis membrane with a molecular weight cut-off of 1000 Da, and freeze-drying is carried out to obtain intermediate 3;

[0044] (3) intermediate 3 (5g) in step (2) is added into 120 mL of acetone, then epichlorohydrin (2.5g) and sodium hydroxide (0.25g) are added, reaction is carried out at 55°C for 4.5h, after reaction is completed, water is added to the reaction solution, the organic layer is separated, and anhydrous magnesium sulfate is used for drying, and the epoxy functionalized siloxane resin is obtained; the GPC of the obtained epoxy functionalized siloxane resin is Mn=5318g / mol.

[0045] The embodiment 2 also provides a preparation method of the high-adhesion anti-aging ceramic tile glue, and the preparation method is specifically as follows:

[0046] According to the weight parts, the components are uniformly mixed, stirred at a speed of 200 rpm for 35 min, and the high-adhesion anti-aging ceramic tile glue is obtained after discharging.

[0047] Embodiment 3

[0048] The embodiment 3 provides a high-adhesion anti-aging ceramic tile glue, which is composed of the following components in terms of weight parts: 50 parts of epoxy-functionalized siloxane resin, 60 parts of P.042.5 ordinary portland cement, 20 parts of triethylenetetramine, 10 parts of hydroxypropyl methylcellulose, 5 parts of antioxidant GA-80 (CAS No. 90498-90-1), and 30 parts of fillers (which are compounded by basalt fibers and wollastonite fibers in a weight ratio of 1:0.8); the structural formula of the epoxy-functionalized siloxane resin is the same as that in the embodiment 1.

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

[0050] (1) polycarbonate diol (12 mmol), toluene-2,4-diisocyanate (25 mmol) are added into a flask, then dibutyltin dilaurate (0.1 mmol) is added, and reaction is carried out at 95°C under nitrogen protection for 2h, then 4,4'-diamino diphenyl disulfide (12 mmol) and toluene-2,4-diisocyanate (13 mmol) are added and reaction is continued for 3h, after reaction is completed, 100mL of acetone is added for dilution to obtain a reaction solution of intermediate 1; 20mL of 0.25mmol / L γ-aminopropyl triethoxysilane acetone solution is added dropwise to the above reaction solution under the condition of 95°C for 1.5h, after reaction is completed, the temperature is lowered to room temperature to obtain a reaction solution of intermediate 2;

[0051] (2) the volume ratio of the reaction solution of intermediate 2 to sodium bicarbonate solution is 1:10, 0.1mol / L sodium bicarbonate solution is added to the reaction solution of intermediate 2 obtained in step (1) and stirred for 26h, after reaction is completed, dialysis is carried out for 24h using a dialysis membrane with a molecular weight cut-off of 1000Da, and freeze-drying is carried out to obtain intermediate 3;

[0052] (3) intermediate 3 (5g) of step (2) is added to 160mL of acetone, then epichlorohydrin (6.5g) and sodium hydroxide (0.65g) are added, and reaction is carried out at 65°C for 3.5h, after reaction is completed, water is added to the reaction solution, the organic layer is separated, and anhydrous magnesium sulfate is used for drying to obtain the epoxy-functionalized siloxane resin; the GPC of the obtained epoxy-functionalized siloxane resin is Mn=5230g / mol.

[0053] The embodiment 3 also provides a preparation method of the high-adhesion anti-aging ceramic tile glue as above, and specifically as follows.

[0054] According to the weight fractions, the components are uniformly mixed, stirred at a speed of 250 rpm for 25 min, and the high-adhesion anti-aging ceramic tile glue is obtained after discharging.

[0055] Comparative example

[0056] Comparative example 1

[0057] Comparative example 1 and embodiment 1 differ in that the epoxy functionalized siloxane resin is replaced by an epoxy resin, and the rest is the same as embodiment 1.

[0058] Comparative example 2

[0059] Comparative example 2 and embodiment 1 differ in that the antioxidant is omitted, and the rest is the same as embodiment 1.

[0060] Experimental example

[0061] The properties of the ceramic tile glue obtained in embodiments 1-3 and comparative examples 1-2 are detected according to the detection method in JC / T 547-2017 “Ceramic Wall and Floor Tile Adhesive”, and the results are shown in Table 1.

[0062] Table 1

[0063]

[0064]

[0065] As can be seen from Table 1, the ceramic tile glue obtained in embodiments 1-3 has excellent bonding strength and anti-aging properties. Compared with embodiment 1, comparative example 1 replaces the epoxy functionalized siloxane resin with an epoxy resin, and comparative example 2 omits the antioxidant. By comparing the data of embodiment 1 with comparative examples 1-2, it can be seen that the use of the epoxy functionalized siloxane resin and the antioxidant in the present application can significantly improve the bonding strength and anti-aging properties of the ceramic tile glue. The reason is that the antioxidant can form a hydrogen bond with the carbonyl group in the epoxy functionalized siloxane resin, thereby improving the anti-aging effect; the epoxy functionalized siloxane resin forms a high cross-linking density network when used with the hardening agent, thereby significantly improving the bonding strength of the ceramic tile glue.

[0066] The above embodiments are only preferred embodiments of the present application, and cannot be used to limit the scope of protection of the present application. Any non-essential changes and substitutions made by those skilled in the art on the basis of the present application are within the scope of the present application.

Claims

1. A high adhesive anti-aging tile adhesive, characterized by, By weight parts, including the following components: epoxy functionalized siloxane resin 10-50 parts, cement 40-60 parts, hardening agent 5-20 parts, thickening agent 5-10 parts, antioxidant 1-5 parts, filler 20-30 parts; the structural formula of the epoxy functionalized siloxane resin is as follows: ； The preparation process of the epoxy functionalized siloxane resin is as follows: (1) The polycarbonate diol, toluene-2, 4-diisocyanate and dibutyl tin dilaurate were mixed and heated to react for 2-3h under inert gas atmosphere, then 4, 4'-diamino diphenyl disulfide and toluene-2, 4-diisocyanate were added and continued to react for 2-3h, after the reaction was completed, acetone was added for dilution to obtain the reaction solution of intermediate 1; the reaction solution of intermediate 1 was added with the acetone solution of γ-aminopropyl triethoxysilane for stirring reaction, after the reaction was completed, the reaction solution of intermediate 2 was obtained; (2) The reaction solution of intermediate 2 was added with sodium bicarbonate solution for stirring reaction, after the reaction was completed, the reaction solution was dialyzed and freeze-dried to obtain intermediate 3; (3) The intermediate 3 of step (2) was added into acetone, then epoxy chloropropane and sodium hydroxide were added for reaction, after the reaction was completed, the reaction solution was purified to obtain the epoxy functionalized siloxane resin; The molar ratio of dibutyl tin dilaurate, polycarbonate diol, 4, 4'-diamino diphenyl disulfide and γ-aminopropyl triethoxysilane in step (1) was (0.03-0.1): (8-12): (8-12): 0.005; the total of toluene-2, 4-diisocyanate added twice in step (1) and polycarbonate diol had a molar ratio of (25-38): (8-12); the concentration of γ-aminopropyl triethoxysilane in the acetone solution of γ-aminopropyl triethoxysilane was 0.25mmol / L; The temperature of the heating reaction in step (1) was 85-95℃, and the heating reaction time was 3-5h; the stirring reaction time was 0.5-1.5h; The volume ratio of the reaction solution of intermediate 2 and sodium bicarbonate solution in step (2) was 1: (5-10); the concentration of sodium bicarbonate solution was 0.1mol / L; the stirring reaction time was 22-26h; The dosage ratio of intermediate 3, epoxy chloropropane and sodium hydroxide in step (3) was 1: (0.5-1.5): (0.05-0.15); the reaction temperature was 55-65℃, and the reaction time was 3.5-4.5h.

2. The high-tack, anti-aging tile adhesive of claim 1, wherein, The antioxidant was antioxidant GA-80, the hardening agent was triethylene tetramine or diethylene triamine, and the thickening agent was hydroxypropyl methyl cellulose or hydroxyethyl methyl cellulose.

3. The high-tack, anti-aging tile adhesive of claim 1, wherein, The filler was compounded by basalt fiber and wollastonite fiber at a weight ratio of 1: (0.5-0.8); the cement was Portland cement.

4. The method of producing a high adhesive anti-aging tile adhesive according to any one of claims 1 to 3, wherein Including the following steps: According to the weight parts, the components were mixed uniformly and stirred, and after discharging, the high adhesive anti-aging ceramic tile glue was obtained.

5. The preparation method of the high-adhesion anti-aging tile adhesive as described in claim 4, characterized in that, The stirring speed was 200-250rpm, and the stirring time was 25-35min.

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