Modified antifungal agent, antifungal sealant and preparation method thereof

Abstract

The application discloses a modified mildew-proof agent, a mildew-proof sealant and a preparation method of the mildew-proof sealant. The modified mildew-proof agent is obtained by the reaction of an alkali metal salt of 1,2-benzisothiazolin-3-one and chlorotrimethoxysilane. The mildew-proof sealant comprises an A component and a B component. The A component is prepared from raw materials comprising silane modified polyether, reinforcing filler, fumed silica, thixotropic agent, the modified mildew-proof agent, light stabilizer and plasticizer. The B component is prepared from raw materials comprising reinforcing filler, plasticizer, coupling agent and catalyst. The modified mildew-proof agent greatly improves the compatibility with the silane modified polyether resin, and when added into the silane modified polyether resin, the mechanical strength and other comprehensive properties of the obtained mildew-proof sealant are not affected, the mildew-proof effect is greatly improved, the obtained mildew-proof sealant has excellent mechanical properties, good elasticity, good mildew-proof performance and good yellowing resistance.

Description

Modified anti-mildew agents, anti-mildew grout sealants and their preparation methods Technical Field

[0001] This invention relates to the field of tile grout, and in particular to a modified anti-mildew agent, an anti-mildew tile grout, and a method for preparing the same. Background Technology

[0002] Traditional tile grout is generally based on a two-component epoxy system. This type of grout is typically hard, has poor elasticity, is brittle, and has relatively poor resistance to yellowing. Over time, due to thermal expansion and contraction, internal stress can easily cause problems such as tile cracking and grout cracking. Furthermore, when used in kitchens, bathrooms, and balconies, the humid environment can easily lead to mold growth.

[0003] To address these issues, some research has been conducted in existing technologies. For example, patent CN116285822A uses nanofibers for toughening and carbon black as a reinforcing filler to prepare a mildew-resistant two-component epoxy grout. However, it still cannot prevent excessive internal stress from causing tile cracking and does not solve the yellowing problem. Patent CN116265555A adds high-temperature fillers, which improves the high-temperature resistance and wear resistance of the epoxy grout and makes it less prone to cracking, but it does not solve the mildew resistance and yellowing resistance. Summary of the Invention

[0004] Based on this, the purpose of this invention is to provide a mildew-resistant grout that is resistant to yellowing, has good elasticity, and good mildew resistance.

[0005] To achieve the above-mentioned objectives, the present invention first provides a modified anti-mildew agent that has good compatibility with silane-modified polyether resin. When combined with silane-modified polyether resin, it can be used to prepare an anti-mildew grout sealant that is resistant to yellowing, has good elasticity, and good anti-mildew properties.

[0006] The modified antifungal agent of the present invention includes the following technical solutions.

[0007] A modified antifungal agent has the following structure:

[0008]

[0009] A modified antifungal agent is obtained by reacting an alkali metal salt of 1,2-benzisothiazolin-3-one with trimethoxychlorosilane.

[0010] In some embodiments, the alkali metal salt of the 1,2-benzisothiazolin-3-one is a sodium salt of the 1,2-benzisothiazolin-3-one, having the following structure:

[0011]

[0012] In some embodiments, the molar ratio of the alkali metal salt of the 1,2-benzisothiazolin-3-one to trimethoxychlorosilane is 1:(1.05-1.6).

[0013] In some embodiments, the molar ratio of the alkali metal salt of the 1,2-benzisothiazolin-3-one to trimethoxychlorosilane is 1:(1.1 to 1.3).

[0014] In some embodiments, the molar ratio of the alkali metal salt of the 1,2-benzisothiazolin-3-one to trimethoxychlorosilane is 1:1.2.

[0015] The present invention also provides a method for preparing the modified antifungal agent, including the following technical solution.

[0016] A method for preparing the modified antifungal agent includes the following steps:

[0017] The modified antifungal agent is obtained by reacting the alkali metal salt of the 1,2-benzisothiazolin-3-one with trimethoxychlorosilane in an aprotic solvent.

[0018] In some embodiments, the aprotic polar solvent is benzene and / or toluene.

[0019] In some embodiments, the reaction is carried out at a temperature of 40°C-90°C for 1-5 hours.

[0020] In some embodiments, the reaction is carried out at a temperature of 60°C-80°C for 2-3 hours.

[0021] In some embodiments, the reaction is carried out at a temperature of 70°C for 2.5 hours.

[0022] In some embodiments, the method for preparing the alkali metal salt of 1,2-benzisothiazolin-3-one includes the following steps:

[0023] 1,2-Benzisothiazolin-3-one was reacted with NaCO3 to obtain the alkali metal salt of 1,2-benzisothiazolin-3-one.

[0024] In some embodiments, the molar ratio of 1,2-benzisothiazolin-3-one to NaCO3 is 1:(1.2 to 1.5).

[0025] In some embodiments, the molar ratio of 1,2-benzisothiazolin-3-one to NaCO3 is 1:1.3.

[0026] In some of the embodiments, the solvent for the reaction of 1,2-benzisothiazolin-3-one with NaCO3 is benzene and / or toluene.

[0027] In some of these embodiments, the reaction of 1,2-benzisothiazolin-3-one with NaCO3 is carried out at a temperature of 40°C-80°C for 1-3 hours.

[0028] In some of these embodiments, the reaction of 1,2-benzisothiazolin-3-one with NaCO3 is carried out at a temperature of 50°C-70°C for 1-3 hours.

[0029] In some of these embodiments, the reaction of 1,2-benzisothiazolin-3-one with NaCO3 was carried out at 60°C for 1.5 h.

[0030] The present invention also provides the application of the modified anti-mildew agent in the preparation of anti-mildew grout.

[0031] This invention also provides an anti-mildew grout sealant, which not only has excellent anti-mildew effect, but also excellent yellowing resistance, good elasticity, high mechanical strength, high hardness, suitable surface drying time, good workability and adhesion, and low VOC, with excellent environmental performance.

[0032] The anti-mildew grout sealant of the present invention includes the following technical solutions.

[0033] A mildew-resistant grout sealant, comprising component A and component B, wherein component A is prepared from raw materials comprising the following components:

[0034]

[0035]

[0036] Component B is prepared from raw materials comprising the following components:

[0037]

[0038] In some embodiments, component A is prepared from raw materials comprising the following components, in parts by weight:

[0039]

[0040] Component B is prepared from raw materials comprising the following components:

[0041]

[0042] In some embodiments, component A is prepared from raw materials comprising the following components, in parts by weight:

[0043]

[0044]

[0045] Component B is prepared from raw materials comprising the following components:

[0046]

[0047] In some embodiments, the volume ratio of component A to component B is 1:0.8-1.2 when used.

[0048] In some embodiments, the silane-modified polyether is selected from one or more combinations of Kaneka Chemical's SAX750, SAX400, SAX575, SAX530, SAX580, SAX590 and Wacker's XT 55, STP-E10, STP-E15, STP-E30, STP-E35, XB502.

[0049] In some embodiments, the silane-modified polyether is a combination of STP-E35 and XB502 in a mass ratio of 1:0.8-1.2.

[0050] In some embodiments, the silane-modified polyether is a combination of STP-E10, STP-E30 and XB502 in a mass ratio of 1:1.5-2.5:1.5-2.5.

[0051] In some embodiments, the reinforcing filler in component A is selected from one or more combinations of nano-calcium carbonate, heavy calcium carbonate, silica powder, diatomaceous earth, talc, and kaolin.

[0052] In some embodiments, the reinforcing filler in component A is a combination of nano-calcium carbonate and heavy calcium carbonate in a mass ratio of 1:2-3.

[0053] In some embodiments, the thixotropic agent is selected from one or more combinations of polyamide wax, hydrogenated castor oil, and nano-sized diatomaceous earth.

[0054] In some embodiments, the light stabilizer is one or more combinations of BASF's Tinuvin UV-P, Tinuvin UV-9, Tinuvin 326, Tinuvin, Tinuvin 540 and Tinuvin 770.

[0055] In some embodiments, the light stabilizer is a combination of Tinuvin UV-9 and Tinuvin UV-P in a mass ratio of 1:2-3.

[0056] In some embodiments, the light stabilizer is a combination of Tinuvin 326 and Tinuvin 770 in a mass ratio of 1:0.8-1.2.

[0057] In some embodiments, the plasticizer in component A is a phthalate plasticizer and / or a polyether polyol plasticizer.

[0058] In some embodiments, the phthalate plasticizer is diisodecyl phthalate.

[0059] In some embodiments, the polyether polyol plasticizer is PPG-1000, PPG-2000, and / or PPG-3000.

[0060] In some embodiments, the reinforcing filler in component B is selected from one or more combinations of nano-calcium carbonate, heavy calcium carbonate, silica powder, diatomaceous earth, talc, and kaolin.

[0061] In some embodiments, the coupling agent is selected from one or more combinations of γ-aminopropyltriethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, and γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0062] In some embodiments, the catalyst is selected from one or more combinations of dibutyltin dilaurate, dioctyltin diacetate, chelated tin, stannous octoate, and organotin bis(β-diketone).

[0063] In some embodiments, the plasticizer in component B is a phthalate plasticizer and / or a polyether polyol plasticizer.

[0064] In some embodiments, the phthalate plasticizer is diisodecyl phthalate.

[0065] In some embodiments, the polyether polyol plasticizer is PPG-1000, PPG-2000, and / or PPG-3000.

[0066] The present invention also provides a method for preparing the anti-mildew sealant, including the following technical solution.

[0067] A method for preparing an anti-mildew grout sealant, comprising the following steps:

[0068] Preparation of component A: The silane-modified polyether, reinforcing filler, fumed silica, thixotropic agent, modified mildew inhibitor, light stabilizer and plasticizer are added to a planetary mixer and mixed for 60 min to 180 min at a temperature of 60℃~120℃ and a vacuum degree of -0.06~-0.099MPa. After cooling, component A is obtained.

[0069] Preparation of component B: The reinforcing filler, plasticizer, coupling agent and catalyst are added to a high-speed disperser and stirred for 30 min to 80 min under a vacuum of -0.06 to -0.099 MPa. After cooling, component B is obtained.

[0070] In some embodiments, the preparation method of the anti-mildew grout includes the following steps:

[0071] Preparation of component A: The silane-modified polyether, reinforcing filler, fumed silica, thixotropic agent, modified mildew inhibitor, light stabilizer and plasticizer are added to a planetary mixer and mixed for 120 min to 180 min at a temperature of 95℃~105℃ and a vacuum degree of -0.08~-0.099MPa. After cooling, component A is obtained.

[0072] Preparation of component B: The reinforcing filler, plasticizer, coupling agent and catalyst are added to a high-speed disperser and stirred for 50 min to 70 min under a vacuum of -0.08 to -0.099 MPa. After cooling, component B is obtained.

[0073] This invention uses silane-modified polyether resin as the base polymer and combines it with a specifically modified antifungal agent to prepare a silane-modified polyether antifungal grout sealant with good yellowing resistance, elasticity, and antifungal effect. This invention modifies the conventional antifungal agent 1,2-benzisothiazolin-3-one. The antifungal agent specifically modified in this invention significantly improves its compatibility with silane-modified polyether resin. Adding it to the silane-modified polyether resin can greatly improve its antifungal effect without affecting the mechanical strength and other comprehensive properties of the resulting grout sealant. Therefore, the resulting antifungal grout sealant has excellent mechanical properties, good elasticity, good antifungal performance, and good yellowing resistance. The antifungal grout sealant of this invention, with the synergistic effect of its components in a specific ratio, has the following beneficial effects:

[0074] 1. The two-component silane-modified polyether anti-mildew grout of the present invention has better elasticity than epoxy grout, is more resistant to bending and scratching, has less internal stress, is less prone to cracking problems common in grout, and will not cause damage to tiles due to displacement or other reasons.

[0075] 2. The two-component silane-modified polyether anti-mold grout of the present invention, by adding a specific modified anti-mold agent, has a good anti-mold effect and can prevent mold for a long time, solving the problem that grout is prone to mold growth in kitchen and bathroom applications due to the humid environment.

[0076] 3. The two-component silane-modified polyether anti-mildew grout of the present invention has superior yellowing resistance, low VOC, and excellent environmental performance compared with traditional epoxy grout. It is environmentally friendly and aesthetically pleasing, and has a greater prospect in the field of grout. Detailed Implementation

[0077] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are merely illustrative of the present invention and should not be construed as limiting the invention.

[0078] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0079] The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, apparatus, product, or device that includes a series of steps is not limited to the steps or modules listed, but may optionally include steps not listed, or may optionally include other steps inherent to such process, method, product, or device.

[0080] In this invention, "multiple" refers to two or more. "And / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0081] The modified antifungal agent used in the following examples is prepared by the following method:

[0082] 1 mol of 1,2-benzisothiazolin-3-one and 1.3 mol of NaCO3 were added to 500 ml of benzene solvent and reacted at 60 °C for 1.5 h. Then, 1.2 mol of trimethoxychlorosilane was added to the resulting reaction mixture and reacted at 70 °C for 2.5 h. After distillation, approximately 232 g of the modified antifungal agent product was obtained, with a yield of 85%.

[0083] The reaction principle is as follows:

[0084]

[0085] The obtained modified antifungal agent product was found to have a concentration at 2820 cm⁻¹ using infrared spectroscopy. -1 The characteristic peak of -OCH3 appears at 910 cm⁻¹. -1 The presence of N-Si absorption peaks indicates that the modified antifungal agent with the above structure has been successfully prepared.

[0086] All parts of raw materials mentioned in the following examples are by weight.

[0087] Example 1

[0088] This embodiment provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0089] The preparation method of component A is as follows:

[0090] Take 100 parts of silane-modified polyether (composed of 50 parts of Kaneka Chemical's SAX400 and 50 parts of Kaneka Chemical's SAX750), 70 parts of heavy calcium carbonate, 20 parts of fumed silica, 3 parts of polyamide wax, 8 parts of Tinuvin 326, 0.2 parts of modified antifungal agent, and 30 parts of PPG-3000 and add them to a planetary mixer. Mix for 100 min at a temperature of 70℃, a vacuum of -0.07MPa, and a stirring frequency of 30Hz. Cool to room temperature to obtain component A.

[0091] The preparation method of component B is as follows:

[0092] Take 60 parts of kaolin, 40 parts of PPG-2000, 8 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 0.5 parts of chelated tin and add them to a high-speed disperser. Stir and mix for 60 minutes under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0093] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0094] Example 2

[0095] This embodiment provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0096] The preparation method of component A is as follows:

[0097] Take 100 parts of silane-modified polyether (composed of 50 parts of Wacker's STP-E35 and 50 parts of Wacker's XB502), 60 parts of nano-calcium carbonate, 10 parts of fumed silica, 5 parts of Tinuvin UV-P, 2 parts of Tinuvin UV-9, 3 parts of modified antifungal agent, and 20 parts of PPG-1000 and add them to a planetary mixer. Mix for 180 min at a temperature of 105℃, a vacuum of -0.09MPa, and a stirring frequency of 30Hz. Cool to room temperature to obtain component A.

[0098] The preparation method of component B is as follows:

[0099] Take 20 parts of heavy calcium carbonate, 10 parts of nano calcium carbonate, 30 parts of PPG-2000, 10 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and 1 part of dibutyltin dilaurate and add them to a high-speed disperser. Stir and mix for 60 min under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0100] The preparation method of the two-component silane-modified polyether grout sealant is as follows:

[0101] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0102] Example 3

[0103] This embodiment provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0104] The preparation method of component A is as follows:

[0105] 100 parts of silane-modified polyether (composed of 20 parts of Wacker's STP-E10, 40 parts of Wacker's STP-E30 and 40 parts of Wacker's XB502), 20 parts of nano-calcium carbonate, 50 parts of heavy calcium carbonate, 20 parts of fumed silica, 3 parts of Tinuvin 326, 3 parts of Tinuvin 770, 0.7 parts of modified antifungal agent, and 25 parts of diisodecyl phthalate were added to a planetary mixer and mixed for 120 min at a temperature of 95℃, a vacuum of -0.09 MPa and a stirring frequency of 30 Hz. The mixture was then cooled to room temperature to obtain component A.

[0106] The preparation method of component B is as follows:

[0107] Take 60 parts of diatomaceous earth, 30 parts of PPG-2000, 7 parts of N-aminoethyl-γ-aminopropyltriethoxysilane, and 0.7 parts of dibutyltin dilaurate and add them to a high-speed disperser. Stir and mix for 60 minutes under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0108] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0109] Example 4

[0110] This embodiment provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0111] The preparation method of component A is as follows:

[0112] Take 100 parts of silane-modified polyether (composed of 40 parts of Kaneka Chemical's SAX575, 40 parts of Kaneka Chemical's SAX530 and 20 parts of Wacker's STP-E35), 50 parts of heavy calcium carbonate, 30 parts of fumed silica, 9 parts of Tinuvin 770, 0.5 parts of modified antifungal agent, and 15 parts of PPG-1000, add them to a planetary mixer, mix for 80 min at a temperature of 75℃, a vacuum of -0.06MPa and a stirring frequency of 30Hz, and cool to room temperature to obtain component A.

[0113] The preparation method of component B is as follows:

[0114] Take 60 parts of kaolin, 40 parts of PPG-2000, 6 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 1 part of dibutyltin dilaurate and add them to a high-speed disperser. Stir and mix for 80 minutes under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0115] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0116] Example 5

[0117] This embodiment provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0118] The preparation method of component A is as follows:

[0119] Take 100 parts of silane-modified polyether (composed of 20 parts of Kaneka Chemical's SAX575, 20 parts of Wacker's STP-E35 and 60 parts of Wacker's XB502), 50 parts of kaolin, 30 parts of fumed silica, 5 parts of Tinuvin 326, 5 parts of Tinuvin 770, 2 parts of modified antifungal agent, and 20 parts of PPG-3000 and add them to a planetary mixer. Mix for 120 min at a temperature of 65℃, a vacuum of -0.06MPa and a stirring frequency of 30Hz. Cool to room temperature to obtain component A.

[0120] The preparation method of component B is as follows:

[0121] Take 50 parts of heavy calcium carbonate, 20 parts of PPG-3000, 10 parts of N-aminoethyl-γ-aminopropyltrimethoxysilane, and 1.5 parts of dibutyltin dilaurate and add them to a high-speed disperser. Stir and mix for 60 minutes under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0122] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0123] Comparative Example 1

[0124] This comparative example provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0125] The preparation method of component A is as follows:

[0126] 100 parts of silane-modified polyether (composed of 20 parts of Wacker's STP-E10, 40 parts of Wacker's STP-E30 and 40 parts of Wacker's XB502), 20 parts of nano-calcium carbonate, 50 parts of heavy calcium carbonate, 20 parts of fumed silica, 3 parts of Tinuvin 326, 3 parts of Tinuvin 770, 0.7 parts of antifungal agent 1,2-benzisothiazolin-3-one, and 25 parts of diisodecyl phthalate were added to a planetary mixer and mixed for 120 min at a temperature of 95℃, a vacuum of -0.09 MPa and a stirring frequency of 30 Hz. The mixture was then cooled to room temperature to obtain component A.

[0127] The preparation method of component B is as follows:

[0128] Take 60 parts of diatomaceous earth, 30 parts of PPG-2000, 7 parts of N-aminoethyl-γ-aminopropyltriethoxysilane, and 0.7 parts of dibutyltin dilaurate and add them to a high-speed disperser. Stir and mix for 60 minutes under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0129] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0130] Comparative Example 2

[0131] This comparative example provides a two-component epoxy grout sealant, consisting of component A and component B.

[0132] The preparation method of component A is as follows:

[0133] Take 100 parts of bisphenol A epoxy resin, 10 parts of fumed silica, 6 parts of Tinuvin 770, 1 part of diluent, and 0.5 parts of defoamer, add them to a planetary mixer, mix for 100 min at a temperature of 75℃, a vacuum of -0.07MPa, and a stirring frequency of 30Hz, and cool to room temperature to obtain component A.

[0134] The preparation method of component B is as follows:

[0135] Take 90 parts of curing agent, 6 parts of Tinuvin 326, 1 part of diluent and 8 parts of fumed silica and add them to a planetary mixer. Stir and mix for 60 min under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0136] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0137] Comparative Example 3

[0138] This comparative example provides a two-component silane-modified polyether anti-mildew grout sealant, consisting of component A and component B.

[0139] The preparation method of component A is as follows:

[0140] 100 parts of silane-modified polyether (composed of 20 parts of Wacker's STP-E10, 40 parts of Wacker's STP-E30 and 40 parts of Wacker's XB502), 20 parts of nano-calcium carbonate, 50 parts of heavy calcium carbonate, 20 parts of fumed silica, 3 parts of Tinuvin 326, 3 parts of Tinuvin 770, 0.7 parts of modified antifungal agent, and 25 parts of diisodecyl phthalate were added to a planetary mixer and mixed for 120 min at a temperature of 95℃, a vacuum of -0.09 MPa and a stirring frequency of 30 Hz. The mixture was then cooled to room temperature to obtain component A.

[0141] The preparation method of component B is as follows:

[0142] Take 60 parts of diatomaceous earth, 30 parts of PPG-2000, 7 parts of N-aminoethyl-γ-aminopropyltriethoxysilane, and 0.7 parts of dibutyltin dilaurate and add them to a high-speed disperser. Stir and mix for 60 minutes under a vacuum of -0.09 MPa and a stirring speed of 600 rpm. Cool to room temperature to obtain component B.

[0143] When using, mix component A and component B thoroughly at a volume ratio of 1:1.

[0144] The difference between the synthesis method of the modified antifungal agent in this comparative example and the synthesis method of the modified antifungal agent in the examples is that trimethylchlorosilane is used instead of trimethoxychlorosilane, while the other raw materials and preparation methods are the same as in the examples.

[0145] The following performance tests were conducted on the grout prepared in Examples 1-5 and Comparative Examples 1-3:

[0146] 1. Surface drying time: determined according to the method in GB / T 13477.5.

[0147] 2. Tensile strength: Tested in accordance with GB / T 528-2009, using type 1 dumbbell-shaped specimens.

[0148] 3. Elongation at break: Tested according to GB / T 528-2009, using type 1 dumbbell-shaped specimens.

[0149] 4. Hardness: Tested according to GB / T 2411 using a Type D Shore hardness tester.

[0150] 5. Abrasion resistance: Tested according to 6.4.7 of T / CBMF 166-2022.

[0151] 6. Stain resistance: Tested in accordance with 6.4.9 of T / CBMF 166-2022.

[0152] 7. Flexibility of the rubber strip: Prepare a rubber strip with a diameter of 2mm±0.1mm, cure it for 168h, bend the rubber strip at 180° and observe the surface of the rubber strip.

[0153] 8. Artificial climate aging: The gel sample was prepared into a 100mm*100mm*6mm film and cured under standard conditions for 144 hours. Then, the test was carried out according to GB / T 16422.2-2014, with a cumulative irradiation time of 168 hours.

[0154] 9. Anti-mildew properties: Tested according to GB / T 1741-2020.

[0155] 10. VOC: Tested in accordance with GB 18583.

[0156] Table 1 Performance test results of tile grout

[0157]

[0158]

[0159] The test results are shown in Table 1. A comparison of Comparative Example 2 and Example 3 shows that the polyether-based grout has a higher elongation at break compared to the epoxy-based grout, indicating better elasticity. Therefore, in the strip flexibility test, no cracks were found in the grout strips prepared in Example 2; while Comparative Example 2 showed creases and shallow cracks. Furthermore, during artificial climate aging, it was found that the grout in Comparative Example 2 was prone to discoloration, classified as level 2, while the grouts in the examples were all classified as level 0.

[0160] The anti-mold effect shows that the modified anti-mold agent prepared in this invention can achieve a level 0 anti-mold effect in the resulting grout with only a small amount added, while Comparative Example 2 can only achieve level 2. The only difference between Example 3 and Comparative Example 1 is whether the added anti-mold agent is modified. Compared with Example 3, Comparative Example 3 uses different raw materials for modifying the anti-mold agent. It can be seen that the modified anti-mold agent prepared in this invention has a more significant anti-mold effect than the unmodified anti-mold agent and the modified anti-mold agent prepared in Comparative Example 3, without affecting the mechanical properties and other comprehensive properties of the resulting grout. This is because the modified anti-mold agent prepared in Comparative Example 3 and the unmodified anti-mold agent have poor compatibility with silane-modified polyether, resulting in a significantly prolonged surface drying time, significantly reduced hardness and tensile strength of the grout, and a reduced anti-mold effect due to compatibility issues. It is evident that by modifying the antifungal agent 1,2-benzisothiazolin-3-one with trimethoxychlorosilane, the compatibility of the antifungal agent in silane-modified polyether can be greatly improved, thereby significantly enhancing its antifungal effect without reducing the overall performance of the sealant, such as its mechanical strength.

[0161] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0162] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A modified antifungal agent, characterized in that, It has the following structure:

2. A method for preparing the modified antifungal agent according to claim 1, characterized in that, The process includes the following steps: reacting an alkali metal salt of 1,2-benzisothiazolin-3-one with trimethoxychlorosilane in an aprotic solvent to obtain the modified antifungal agent.

3. The method for preparing the modified antifungal agent according to claim 2, characterized in that, The alkali metal salt of the 1,2-benzisothiazolin-3-one is a sodium salt of the 1,2-benzisothiazolin-3-one; and / or, the molar ratio of the alkali metal salt of the 1,2-benzisothiazolin-3-one to trimethoxychlorosilane is 1:(1.05-1.6).

4. The method for preparing the modified antifungal agent according to claim 2, characterized in that, The aprotic solvent is benzene and / or toluene; and / or, the reaction temperature is 40℃-90℃ and the time is 1h-5h.

5. The method for preparing the modified antifungal agent according to any one of claims 2-4, characterized in that, The preparation method of the alkali metal salt of 1,2-benzisothiazolin-3-one includes the following steps: reacting 1,2-benzisothiazolin-3-one with Na2CO3 to obtain the alkali metal salt of 1,2-benzisothiazolin-3-one.

6. The method for preparing the modified antifungal agent according to claim 5, characterized in that, The molar ratio of 1,2-benzisothiazolin-3-one to Na2CO3 is 1:(1.2-1.5).

7. The method for preparing the modified antifungal agent according to claim 5, characterized in that, The solvent for the reaction of 1,2-benzisothiazolin-3-one with Na2CO3 is benzene and / or toluene.

8. The method for preparing the modified antifungal agent according to claim 5, characterized in that, The reaction temperature of 1,2-benzisothiazolin-3-one with Na2CO3 is 40℃-80℃, and the time is 1h-3h.

9. The application of the modified anti-mildew agent according to claim 1 in the preparation of anti-mildew grout.

10. A mildew-resistant grout sealant, characterized in that, Comprising component A and component B, component A is prepared from raw materials comprising the following components, by weight: Component B is prepared from raw materials comprising the following components:

11. The anti-mildew grout sealant according to claim 10, characterized in that, The silane-modified polyether is selected from one or more combinations of SAX750, SAX400, SAX575, SAX530, SAX580, SAX590 from Kaneka Chemical and XT 55, STP-E10, STP-E15, STP-E30, STP-E35, and XB502 from Wacker Chemie; and / or, the reinforcing filler in component A is selected from one or more combinations of nano-calcium carbonate, heavy calcium carbonate, silica powder, diatomaceous earth, talc, and kaolin; and / or, the thixotropic agent is selected from one or more combinations of polyamide wax, hydrogenated castor oil, and nano-diatomaceous earth; and / or, the light stabilizer is Tinuvin UV-P, Tinuvin UV-9, Tinuvin 326, Tinuvin, Tinuvin 540, and Tinuvin from BASF. One or more combinations of 770; and / or, the plasticizer in component A is a phthalate plasticizer and / or a polyether polyol plasticizer; and / or, the reinforcing filler in component B is selected from one or more combinations of nano-calcium carbonate, heavy calcium carbonate, silica powder, diatomaceous earth, talc, and kaolin; and / or, the coupling agent is selected from γ-aminopropyltriethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, and N-aminoethyl-γ-aminopropyltriethoxysilane. The catalyst is selected from one or more combinations of alkyl and γ-(2,3-epoxypropoxy)propyltrimethoxysilane; and / or, the catalyst is selected from one or more combinations of dibutyltin dilaurate, dioctyltin diacetate, chelated tin, stannous octoate, and organotin bis(β-diketone); and / or, the plasticizer in component B is a phthalate plasticizer and / or a polyether polyol plasticizer; and / or, when used, the mixing volume ratio of component A to component B is 1:0.8-1.

2.

12. A method for preparing the anti-mildew grout sealant according to claim 10 or 11, characterized in that, The process includes the following steps: Preparation of component A: The silane-modified polyether, reinforcing filler, fumed silica, thixotropic agent, modified mildew inhibitor, light stabilizer, and plasticizer are added to a planetary mixer and mixed for 60 min to 180 min at a temperature of 60℃ to 120℃ and a vacuum of -0.06 to -0.099 MPa. After cooling, component A is obtained. Preparation of component B: The reinforcing filler, plasticizer, coupling agent, and catalyst are added to a high-speed disperser and stirred for 30 min to 80 min at a vacuum of -0.06 to -0.099 MPa. After cooling, component B is obtained.

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