Environment-friendly long-acting mildew-proof silane modified polyether sealant and preparation method thereof

Abstract

The application discloses an environment-friendly long-acting mildew-proof silane modified polyether sealant and a preparation method thereof. The silane modified polyether sealant comprises the following raw material components in parts by weight: MS-polymer prepolymer 100 parts, cyclodextrin polyether polyol inclusion compound 4-16 parts, reinforcing filler 180-450 parts, thixotropic agent 1-8 parts, plasticizer 50-400 parts, hydroxyl scavenger 4-16 parts, coupling agent 2-9 parts, and organic tin catalyst 0.1-0.6 parts; the cyclodextrin polyether polyol inclusion compound is obtained by cyclodextrin polyether polyol inclusion natural mildew-proof agent; the cyclodextrin polyether polyol is obtained by reaction of cyclodextrin, diethylene glycol and an oxacyclic compound under alkaline conditions; and the oxacyclic compound is at least one of oxirane, oxetane and tetrahydrofuran. The environment-friendly long-acting mildew-proof silane modified polyether sealant has excellent long-acting mildew-proof effect and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of sealants, and in particular to an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant and its preparation method. Background Technology

[0002] Silane-modified polyether sealant possesses excellent workability, adhesion, and durability, exhibits low environmental pollution, and is paintable, making it widely used in building decoration and renovation. In interior decoration, polyether sealant is commonly used in areas such as kitchens and bathrooms. However, due to the consistently humid environment, coupled with humid weather or hot summers, polyether sealant is susceptible to microbial attack, mold growth, and subsequent mildew and discoloration, which is both unsightly and compromises its waterproofing and sealing performance. To address the mold problem, existing technologies often improve anti-mold performance by directly adding anti-mold agents such as halides, quaternary ammonium salts, and isothiazolinides. However, these anti-mold agents have drawbacks such as toxicity, harm to the environment and human health, instability, or short-lived effects. In response to the call for green environmental protection, it is necessary to provide an environmentally friendly, long-lasting anti-mold polyether sealant. Summary of the Invention

[0003] To overcome the above problems, the purpose of this invention is to provide an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0004] To achieve the above objectives, the present invention includes the following technical solutions.

[0005] An environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant, comprising the following raw material components by weight:

[0006]

[0007]

[0008] The cyclodextrin polyether polyol inclusion complex is obtained by encapsulating a natural antifungal agent in a cyclodextrin polyether polyol;

[0009] The cyclodextrin polyether polyol is obtained by reacting cyclodextrin, diethylene glycol, and oxoheterocyclic compounds under alkaline conditions.

[0010] The oxoheterocyclic compound is at least one of ethylene oxide, propylene oxide, and tetrahydrofuran.

[0011] In some embodiments, the environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant comprises the following raw material components, by weight:

[0012]

[0013] In some embodiments, the environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant comprises the following raw material components, by weight:

[0014]

[0015]

[0016] In some embodiments, the cyclodextrin is one or more combinations of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0017] In some of these embodiments, the cyclodextrin is β-cyclodextrin.

[0018] In some embodiments, the natural antifungal agent is one or more combinations of catechin, eugenol, vanillin, and cinnamic acid; more preferably, it is cinnamic acid.

[0019] In some of these embodiments, the oxocyclic compound is propylene oxide.

[0020] In some embodiments, the mass ratio of the cyclodextrin, diethylene glycol, and oxocyclic compound is 250–450: 125–225: 180–330.

[0021] In some embodiments, the mass ratio of the cyclodextrin, diethylene glycol, and oxoheterocyclic compound is 280–320:140–160:220–280.

[0022] In some embodiments, the mass ratio of the cyclodextrin, diethylene glycol, and oxoheterocyclic compound is 295–305: 145–155: 245–255.

[0023] In some embodiments, the mass ratio of the cyclodextrin, diethylene glycol, and oxocyclic compound is 300:148-152:248-252.

[0024] In some embodiments, the mass ratio of the cyclodextrin polyether polyol to the natural antifungal agent is 1.5 to 3:1.

[0025] In some embodiments, the mass ratio of the cyclodextrin polyether polyol to the natural antifungal agent is 2 to 2.5:1.

[0026] In some embodiments, the preparation method of the cyclodextrin polyether polyol includes the following steps:

[0027] The reaction system containing 250–450 parts by weight of cyclodextrin, 125–225 parts by weight of diethylene glycol, 125–225 parts by weight of water, and 2–5 parts by weight of alkali was purged with nitrogen, then evacuated to -0.09 MPa to -0.1 MPa, heated to 85°C to 95°C, and 180–330 parts by weight of an oxocyclic compound was added. After the addition was complete, the reaction was carried out at 100°C to 110°C and 0.05 MPa to 0.20 MPa for 2–6 hours to remove unreacted oxocyclic compounds, yielding cyclodextrin polyether polyol.

[0028] In some embodiments, the base is potassium hydroxide.

[0029] In some embodiments, the preparation method of the cyclodextrin polyether polyol includes the following steps:

[0030] The reaction system containing 280–320 parts by weight of cyclodextrin, 140–160 parts by weight of diethylene glycol, 140–160 parts by weight of water, and 2–4 parts by weight of alkali was purged with nitrogen, then evacuated to -0.09 MPa to -0.1 MPa, and heated to 85°C to 95°C. 220–280 parts by weight of an oxocyclic compound was added. After the addition was complete, the reaction was carried out at 100°C to 110°C and 0.10 MPa to 0.20 MPa for 2–6 hours to remove unreacted oxocyclic compounds, yielding cyclodextrin polyether polyol.

[0031] In some embodiments, the preparation method of the cyclodextrin polyether polyol includes the following steps:

[0032] The reaction system containing 295–305 parts by weight of cyclodextrin, 145–155 parts by weight of diethylene glycol, 145–155 parts by weight of water, and 2.5–3.5 parts by weight of alkali was purged with nitrogen, then evacuated to -0.09 MPa to -0.1 MPa, and heated to 85°C to 95°C. 245–255 parts by weight of an oxocyclic compound was added. After the addition was complete, the reaction was carried out at 100°C to 110°C and 0.10 MPa to 0.20 MPa for 2–4 hours to remove unreacted oxocyclic compounds, yielding cyclodextrin polyether polyol.

[0033] In some embodiments, the preparation method of the cyclodextrin polyether polyol inclusion complex includes the following steps:

[0034] An alcoholic solution of a natural antifungal agent was added to an aqueous solution of cyclodextrin polyether polyol. The mixture was stirred at 40-60°C for 2-6 hours, then cooled, crystallized, and precipitated. The precipitate was then filtered, washed, and dried to obtain the cyclodextrin inclusion complex.

[0035] In some embodiments, the preparation method of the cyclodextrin polyether polyol inclusion complex includes the following steps:

[0036] An alcoholic solution of a natural antifungal agent was added to an aqueous solution of cyclodextrin polyether polyol. The mixture was stirred at 40-50°C for 4-6 hours, then cooled, crystallized, and precipitated. The precipitate was then filtered, washed, and dried to obtain the cyclodextrin inclusion complex.

[0037] In some embodiments, the cooling temperature is 5°C to 10°C.

[0038] In some embodiments, the concentration of the cyclodextrin polyether polyol in the aqueous solution is 0.1 g / ml to 0.2 g / ml.

[0039] In some embodiments, the concentration of the cyclodextrin polyether polyol in the aqueous solution is 0.1 g / ml to 0.15 g / ml.

[0040] In some embodiments, the concentration of the natural antifungal agent in the alcohol solution is 0.04 g / ml to 0.08 g / ml.

[0041] In some embodiments, the concentration of the natural antifungal agent in the alcohol solution is 0.05 g / ml to 0.07 g / ml.

[0042] In some embodiments, the solvent in the alcohol solution of the natural antifungal agent is ethanol.

[0043] In some embodiments, the MS-polymer prepolymer is a trimethoxysilyl-terminated polyether and / or a triethoxysilyl-terminated polyether. Examples include SAX575, SAX590, SAX510, SAX520, and SAX530 from Kaneka Trading (Shanghai) Co., Ltd., and 30000T, 3368T, 3900, and 350A from Jiangsu Ruiyang Antai New Material Technology Co., Ltd.

[0044] In some embodiments, the reinforcing filler is at least one of nano-calcium carbonate, activated calcium carbonate, and fumed silica.

[0045] In some embodiments, the thixotropic agent is at least one of hydrogenated castor oil and polyamide wax.

[0046] In some embodiments, the plasticizer is at least one of diisodecyl phthalate, diisononyl phthalate, and diisooctyl phthalate.

[0047] In some embodiments, the hydroxyl scavenger is at least one of vinyltrimethoxysilane and hexamethyldisilazane.

[0048] In some embodiments, the coupling agent is at least one selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0049] In some embodiments, the organotin catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, and tin octoate.

[0050] A method for preparing an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant includes the following steps:

[0051] The MS-polymer prepolymer, cyclodextrin polyether polyol inclusion complex, reinforcing filler, thixotropic agent, and plasticizer are dehydrated and blended for 60 to 180 minutes at a temperature of 70℃-130℃ and a vacuum of -0.08MPa to -0.1MPa. After cooling, the hydroxyl scavenger, coupling agent, and organotin catalyst are added, and the mixture is stirred for 30 to 90 minutes at a vacuum of -0.08MPa to -0.1MPa and a stirring speed of 10Hz to 20Hz to obtain the environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0052] To improve the long-lasting anti-mildew effect of silane-modified polyether sealants, the inventors discovered that encapsulating natural anti-mildew agents with cyclodextrin can achieve slow-release of the natural anti-mildew agents and prolong their duration of action. However, during the research process, the inventors found that the hydroxyl groups on the surface of cyclodextrin were too concentrated, resulting in large steric hindrance and uneven dispersion in the silane-modified polyether sealant. The compatibility between the two was poor, and adding a large amount of cyclodextrin led to a decrease in the mechanical properties of the silane-modified polyether sealant and, to some extent, affected its slow-release effect on the natural anti-mildew agents. To solve this problem, the inventors further discovered that cyclodextrin polyether polyols obtained by reacting cyclodextrin, diethylene glycol, and heterocyclic compounds (such as propylene oxide or tetrahydrofuran) under alkaline catalysis can replace cyclodextrin in encapsulating natural anti-mildew agents. Adding the resulting inclusion complex to the modified polyether sealant can effectively improve its mechanical properties and further enhance its long-lasting anti-mildew effect. The cyclodextrin polyether polyol prepared by this invention has more reactive sites and steric ductility than cyclodextrin. It has good compatibility with silane-modified polyether adhesives, resulting in good dispersibility in silane-modified polyether adhesives. This can effectively improve the mechanical properties of the obtained silane-modified polyether sealant, while also giving it a superior long-lasting anti-mildew effect.

[0053] Therefore, the environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant of the present invention has the following beneficial effects:

[0054] The cyclodextrin polyether polyol inclusion complex prepared in this invention exhibits good compatibility with silane-modified polyether sealants and can be dispersed relatively uniformly in the sealant, thereby improving the mechanical properties of the modified polyether sealant. Through the sustained-release effect of the cyclodextrin polyether polyol, the duration of action of the natural antifungal agent is effectively extended. Simultaneously, in combination with MS-polymer prepolymer, reinforcing filler, plasticizer, hydroxyl scavenger, and coupling agent, the prepared environmentally friendly, long-lasting antifungal silane-modified polyether sealant possesses excellent long-lasting antifungal effect and mechanical properties.

[0055] In addition, the present invention uses a natural antifungal agent to overcome the shortcomings of traditional antifungal agents, which are toxic and harmful to the environment and human body. The cyclodextrin polyether polyol inclusion complex of the present invention is environmentally friendly and non-toxic, and its use in sealants can reduce environmental harm. Detailed Implementation

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] The following are specific examples.

[0061] Unless otherwise specified, "parts" in the following examples refer to parts by weight.

[0062] In the following examples, the preparation process of cyclodextrin polyether polyol inclusion complex-1 is as follows:

[0063] (1) Preparation of cyclodextrin polyether polyol: 300g β-cyclodextrin, 150g diethylene glycol, 150g water and 3g potassium hydroxide were replaced with nitrogen and evacuated to -0.098MPa. The temperature was raised to 90℃ and 250g propylene oxide was added. After the addition was complete, the mixture was reacted at 100℃ and 0.15MPa for 3h. Then, the temperature was maintained and unreacted propylene oxide was removed under a vacuum of -0.095MPa to obtain cyclodextrin polyether polyol.

[0064] (2) Preparation of cyclodextrin polyether polyol inclusion complex: 13g of cyclodextrin polyether polyol was dispersed in 100ml of water at 70℃ to obtain a cyclodextrin polyether polyol solution; 6g of cinnamic acid was dissolved in 100ml of ethanol to obtain a cinnamic acid solution. The cinnamic acid solution was added dropwise to the cyclodextrin polyether polyol solution at 50℃ with stirring. After stirring for 5h, the resulting reaction mixture was cooled at 5℃ to crystallize and precipitate. After filtration, the cinnamic acid on the surface was washed away with a 30% (v / v) ethanol solution, dried, crushed, and passed through a 100-mesh sieve to obtain cyclodextrin polyether polyol inclusion complex-1.

[0065] The preparation process of cyclodextrin polyether polyol inclusion complex-2 is as follows:

[0066] (1) Preparation of cyclodextrin polyether polyol: 300g α-cyclodextrin, 150g diethylene glycol, 150g water and 3g potassium hydroxide were replaced with nitrogen and evacuated to -0.098MPa. The temperature was raised to 90℃ and 250g propylene oxide was added. After the addition was complete, the mixture was reacted at 100℃ and 0.15MPa for 3h. Then, the temperature was maintained and unreacted propylene oxide was removed under a vacuum of -0.092MPa to obtain cyclodextrin polyether polyol.

[0067] (2) Preparation of cyclodextrin polyether polyol inclusion complex: 13g of cyclodextrin polyether polyol was dispersed in 100ml of water at 70℃ to obtain a cyclodextrin polyether polyol solution; 6g of cinnamic acid was dissolved in 100ml of ethanol to obtain a cinnamic acid solution. The cinnamic acid solution was added dropwise to the cyclodextrin polyether polyol solution at 50℃ with stirring. After stirring for 5h, the resulting reaction mixture was cooled at 5℃ to crystallize and precipitate. After filtration, the cinnamic acid on the surface was washed away with a 30% (v / v) ethanol solution, dried, crushed, and passed through a 100-mesh sieve to obtain cyclodextrin polyether polyol inclusion complex-2.

[0068] The preparation process of cyclodextrin polyether polyol inclusion complex-3 is as follows:

[0069] (1) Preparation of cyclodextrin polyether polyol: 300g γ-cyclodextrin, 150g diethylene glycol, 150g water and 3g potassium hydroxide were replaced with nitrogen and evacuated to -0.098MPa. The temperature was raised to 90℃ and 250g propylene oxide was added. After the addition was complete, the mixture was reacted at 100℃ and 0.15MPa for 3h. Then, the temperature was maintained and unreacted propylene oxide was removed under a vacuum of -0.098MPa to obtain cyclodextrin polyether polyol.

[0070] (2) Preparation of cyclodextrin polyether polyol inclusion complex: 13 g of cyclodextrin polyether polyol was dispersed in 100 ml of water at 70 °C to obtain a cyclodextrin polyether polyol solution; 6 g of cinnamic acid was dissolved in 100 ml of ethanol to obtain a cinnamic acid solution. The cinnamic acid solution was added dropwise to the cyclodextrin polyether polyol solution at 50 °C with stirring. After stirring for 5 h, the resulting reaction mixture was cooled at 5 °C to crystallize and precipitate. After filtration, the cinnamic acid on the surface was washed away with a 30% (v / v) ethanol solution, dried, crushed, and passed through a 100-mesh sieve to obtain cyclodextrin polyether polyol inclusion complex-3.

[0071] The preparation process of cyclodextrin polyether polyol inclusion complex-4 is as follows:

[0072] (1) Preparation of cyclodextrin polyether polyol: 300g β-cyclodextrin, 150g diethylene glycol, 150g water and 3g potassium hydroxide were replaced with nitrogen and evacuated to -0.098MPa. The temperature was raised to 90℃ and 250g tetrahydrofuran was added. After the addition was complete, the mixture was reacted at 100℃ and 0.15MPa for 3h. Then, the temperature was maintained and unreacted tetrahydrofuran was removed under a vacuum of -0.095MPa to obtain cyclodextrin polyether polyol.

[0073] (2) Preparation of cyclodextrin polyether polyol inclusion complex: 13g of cyclodextrin polyether polyol was dispersed in 100ml of water at 70℃ to obtain a cyclodextrin polyether polyol solution; 6g of cinnamic acid was dissolved in 100ml of ethanol to obtain a cinnamic acid solution. The cinnamic acid solution was added dropwise to the cyclodextrin polyether polyol solution at 50℃ with stirring. After stirring for 5h, the resulting reaction mixture was cooled at 5℃ to crystallize and precipitate. After filtration, the cinnamic acid on the surface was washed away with a 30% (v / v) ethanol solution, dried, crushed, and passed through a 100-mesh sieve to obtain cyclodextrin polyether polyol inclusion complex-4.

[0074] Example 1

[0075] 100 parts of trimethoxysilyl-terminated polyether (SAX510), 15 parts of cyclodextrin polyether polyol inclusion complex-1, 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at -0.099 MPa vacuum and 15 Hz stirring speed to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0076] Example 2

[0077] The difference between this embodiment and Example 1 is that cyclodextrin polyether polyol inclusion complex-2 is added.

[0078] 100 parts of trimethoxysilyl-terminated polyether (SAX510), 15 parts of cyclodextrin polyether polyol inclusion complex-2, 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at -0.099 MPa vacuum and 15 Hz stirring speed to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0079] Example 3

[0080] 100 parts of trimethoxysilyl-terminated polyether (SAX510), 15 parts of cyclodextrin polyether polyol inclusion complex-3, 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at -0.099 MPa vacuum and 15 Hz stirring speed to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0081] Example 4

[0082] 100 parts of trimethoxysilyl-terminated polyether (SAX510), 15 parts of cyclodextrin polyether polyol inclusion complex-4, 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at -0.099 MPa vacuum and 15 Hz stirring speed to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0083] Example 5

[0084] 100 parts of trimethoxysilyl-terminated polyether (SAX520), 10 parts of cyclodextrin polyether polyol inclusion complex-1, 400 parts of activated calcium carbonate, 2 parts of hydrogenated castor oil, and 300 parts of diisononyl phthalate were dehydrated and blended for 110 minutes at 110°C and -0.095 MPa. After cooling, 16 parts of vinyltrimethoxysilane, 9 parts of γ-aminopropyltrimethoxysilane, and 0.6 parts of tin octoate were added and mixed and reacted for 90 minutes under a vacuum of -0.095 MPa and a stirring speed of 20 Hz to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0085] Example 6

[0086] 100 parts of trimethoxysilyl-terminated polyether (3368T), 5 parts of cyclodextrin polyether polyol inclusion complex-1, 300 parts of fumed silica, 8 parts of hydrogenated castor oil, and 200 parts of diisooctyl phthalate were dehydrated and blended for 180 minutes at 90°C and -0.090 MPa. After cooling, 12 parts of hexamethyldisilazane, 2 parts of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.4 parts of dibutyltin diacetate were added and mixed and reacted for 40 minutes under a vacuum of -0.090 MPa and a stirring speed of 10 Hz to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0087] Example 7

[0088] The difference between Example 7 and Example 1 is that eugenol was used instead of cinnamic acid in the preparation of the cyclodextrin polyether polyol inclusion complex.

[0089] Example 8

[0090] The difference between Example 8 and Example 1 is that vanillin was used instead of cinnamic acid in the preparation of the cyclodextrin polyether polyol inclusion complex.

[0091] Example 9

[0092] The difference between Example 9 and Example 1 is that catechin is used instead of cinnamic acid in the preparation of the cyclodextrin polyether polyol inclusion complex.

[0093] Comparative Example 1

[0094] The difference between Comparative Example 1 and Example 1 is that cyclodextrin polyether polyol inclusion complex-1 was not added.

[0095] 100 parts of trimethoxysilyl-terminated polyether (SAX520), 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and a vacuum of -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at a vacuum of -0.099 MPa and a stirring speed of 15 Hz to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0096] Comparative Example 2

[0097] The difference between Comparative Example 2 and Example 1 is that cinnamic acid was used to replace cyclodextrin polyether polyol inclusion complex-1.

[0098] 100 parts of trimethoxysilyl-terminated polyether (SAX520), 15 parts of cinnamic acid, 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at -0.099 MPa vacuum and 15 Hz stirring speed to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0099] Comparative Example 3

[0100] 13 g of β-cyclodextrin was dispersed in 100 ml of water at 70 °C to obtain a cyclodextrin solution; 6 g of cinnamic acid was dissolved in 100 ml of ethanol to obtain a cinnamic acid solution. The cinnamic acid solution was added dropwise to the cyclodextrin solution at 50 °C with stirring. After stirring for 5 h, the resulting reaction mixture was cooled at 5 °C to crystallize and precipitate. The precipitate was filtered, washed with a 30% (v / v) ethanol solution to remove surface cinnamic acid, dried, crushed, and passed through a 100-mesh sieve to obtain the cyclodextrin inclusion complex.

[0101] 100 parts of trimethoxysilyl-terminated polyether (SAX520), 15 parts of cyclodextrin inclusion complex, 200 parts of nano-calcium carbonate, 6 parts of polyamide wax, and 100 parts of diisodecyl phthalate were dehydrated and blended for 120 minutes at 130°C and -0.098 MPa. After cooling, 5 parts of vinyltrimethoxysilane, 6 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and 0.2 parts of dibutyltin dilaurate were added and mixed and reacted for 60 minutes at -0.099 MPa vacuum and 15 Hz stirring speed to obtain an environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealant.

[0102] The silane-modified polyether sealants prepared in Examples 1-9 and Comparative Examples 1-3 were subjected to the following performance tests, using the following methods:

[0103] 1. Tensile strength and elongation at break shall be tested in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber";

[0104] 2. Anti-mold performance was tested according to GB / T 1741 "Determination of Anti-mold Resistance of Coatings". Specifically, after 28 days of culture using the petri dish method, if mold growth is clearly visible to the naked eye on the sample surface and the mold coverage area is greater than 60%, it is classified as Grade 4; if mold growth is clearly visible to the naked eye on the sample surface and the mold coverage area is 30%–60%, it is classified as Grade 3; if mold growth is clearly visible to the naked eye on the sample surface and the mold coverage area is 10%–30%, it is classified as Grade 2; if mold growth is not visible to the naked eye or is difficult to see, but is clearly visible under a magnifying glass, it is classified as Grade 1; if no obvious mold growth is observed on the sample surface under approximately 50x magnification, it is classified as Grade 0. Based on Grade 0, the culture time is further extended, and the mold growth is observed in 28-day cycles. If it remains Grade 0 after one more cycle, it is classified as Grade 2x Grade 0; if it remains Grade 0 after two more cycles, it is classified as Grade 3x Grade 0, and so on. The higher the grade 0 multiple, the longer the anti-mold effect lasts and the better the anti-mold effect.

[0105] The test results are shown in Table 1. As can be seen from Table 1, the environmentally friendly, long-lasting, mildew-resistant silane-modified polyether sealants prepared in all examples meet the application requirements.

[0106] As shown in Example 1 and Comparative Example 1, the cyclodextrin polyether polyol inclusion complex can effectively improve the mildew resistance and mechanical properties of silane-modified polyether sealant. As shown in Example 1 and Comparative Examples 2-3, under the same dosage conditions, the silane-modified polyether sealant with the addition of the cyclodextrin polyether polyol inclusion complex has a higher mildew resistance and superior mechanical properties compared to the addition of the cyclodextrin inclusion complex or a single natural mildew inhibitor. This indicates that the introduction of the cyclodextrin polyether polyol achieves the slow release of the natural mildew inhibitor, effectively prolonging its duration of action. Simultaneously, it exhibits good dispersibility in the silane-modified polyether sealant, effectively improving its mechanical properties.

[0107] As can be seen from Examples 1 and 4, the cyclodextrin polyether polyol prepared using propylene oxide monomer has a higher anti-mildew rating and mechanical properties compared to the cyclodextrin polyether polyol prepared using tetrahydrofuran monomer. This indicates that the monomer structure used in the preparation of cyclodextrin polyether polyol has a certain influence on its sustained-release effect and the improvement of mechanical properties.

[0108] A comparison of Examples 1 and Examples 7-9 reveals that the antifungal effect is best when cinnamic acid is encapsulated in cyclodextrin polyether polyols.

[0109] Table 1

[0110] Tensile strength (MPa) Elongation at break (%) Mildew resistance rating Example 1 1.5 600 5x 0 rating Example 2 1.41 550 4x 0 rating Example 3 1.4 540 4x 0 rating Example 4 1.38 525 3x 0 rating Example 5 1.34 490 3x 0 rating Example 6 1.41 545 2x 0 rating Example 7 1.48 590 3x 0 rating Example 8 1.49 595 2x 0 rating Example 9 1.50 605 3x 0 rating Comparative Example 1 1.15 385 4 rating Comparative Example 2 1.10 360 0 rating Comparative Example 3 1.00 330 2x 0 rating

[0111] 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.

[0112] 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 long-lasting, mildew-resistant silane-modified polyether sealant, characterized in that, By weight, it comprises the following raw material components: 100 parts of MS-polymer prepolymer 4-16 parts of cyclodextrin polyether polyol inclusion complex 180-450 parts of reinforcing filler 1-8 parts of thixotropic agent Plasticizer 50-400 parts 4-16 parts of hydroxyl scavenger 2-9 parts of coupling agent 0.1~0.6 parts of organotin catalyst; The cyclodextrin polyether polyol inclusion complex is obtained by encapsulating a natural antifungal agent in a cyclodextrin polyether polyol; The cyclodextrin polyether polyol is obtained by reacting cyclodextrin, diethylene glycol, and oxoheterocyclic compounds under alkaline conditions. The oxoheterocyclic compound is at least one of ethylene oxide, propylene oxide, and tetrahydrofuran; The mass ratio of the cyclodextrin, diethylene glycol, and oxoheterocyclic compound is 250~450:125~225:180~330; The mass ratio of the cyclodextrin polyether polyol to the natural antifungal agent is 1.5~3:

1.

2. The long-lasting antifungal silane-modified polyether sealant according to claim 1, characterized in that, By weight, it comprises the following raw material components: 100 parts of MS-polymer prepolymer 10-16 parts of cyclodextrin polyether polyol inclusion complex 180-400 parts of reinforcing filler 2-8 parts of thixotropic agent 90-300 parts of plasticizer 4-16 parts of hydroxyl scavenger 5-9 parts of coupling agent 0.1 to 0.6 parts of organotin catalyst.

3. The long-lasting antifungal silane-modified polyether sealant according to claim 1, characterized in that, The cyclodextrin is one or more combinations of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; and / or, The natural antifungal agent is one or more of catechin, eugenol, vanillin, and cinnamic acid.

4. The long-lasting antifungal silane-modified polyether sealant according to claim 3, characterized in that, The cyclodextrin is β-cyclodextrin; and / or, The natural antifungal agent is cinnamic acid; and / or... The oxoheterocyclic compound is propylene oxide; and / or, The mass ratio of the cyclodextrin, diethylene glycol, and oxoheterocyclic compound is 280~320:140~160:220~280; and / or, The mass ratio of the cyclodextrin polyether polyol to the natural antifungal agent is 2~2.5:

1.

5. The long-lasting antifungal silane-modified polyether sealant according to any one of claims 1-4, characterized in that, The preparation method of the cyclodextrin polyether polyol includes the following steps: The reaction system containing 250-450 parts by weight of cyclodextrin, 125-225 parts by weight of diethylene glycol, 125-225 parts by weight of water and 2-5 parts by weight of alkali was purged with nitrogen, then evacuated to -0.09 MPa to -0.1 MPa, heated to 85℃ to 95℃, and 180-330 parts by weight of oxoheterocyclic compounds were added. After the addition was complete, the reaction was carried out at 100℃ to 110℃ and 0.05 MPa to 0.20 MPa for 2-6 hours to remove unreacted oxoheterocyclic compounds, yielding cyclodextrin polyether polyol.

6. The long-lasting antifungal silane-modified polyether sealant according to claim 5, characterized in that, The alkali is potassium hydroxide.

7. The long-lasting anti-mildew silane-modified polyether sealant according to claim 5, characterized in that, The preparation method of the cyclodextrin polyether polyol includes the following steps: The reaction system containing 280-320 parts by weight of cyclodextrin, 140-160 parts by weight of diethylene glycol, 140-160 parts by weight of water and 2-4 parts by weight of alkali was purged with nitrogen, then evacuated to -0.09 MPa to -0.1 MPa, heated to 85℃ to 95℃, and 220-280 parts by weight of oxoheterocyclic compounds were added. After the addition was complete, the reaction was carried out at 100℃ to 110℃ and 0.10 MPa to 0.20 MPa for 2-6 hours to remove unreacted oxoheterocyclic compounds, yielding cyclodextrin polyether polyol.

8. The long-lasting antifungal silane-modified polyether sealant according to any one of claims 1-4, characterized in that, The preparation method of the cyclodextrin polyether polyol inclusion complex includes the following steps: An alcoholic solution of a natural antifungal agent was added to an aqueous solution of cyclodextrin polyether polyol. The mixture was stirred at 40-60°C for 2-6 hours, then cooled, crystallized, and precipitated. The precipitate was then filtered, washed, and dried to obtain the cyclodextrin inclusion complex.

9. The long-lasting antifungal silane-modified polyether sealant according to claim 8, characterized in that, The cooling temperature is 5℃~10℃; and / or, The concentration of the cyclodextrin polyether polyol in the aqueous solution is 0.1 g / ml to 0.2 g / ml; and / or, The concentration of the natural antifungal agent in the alcoholic solution is 0.04 g / ml to 0.08 g / ml; and / or, The solvent in the alcohol solution of the natural antifungal agent is ethanol.

10. The long-lasting antifungal silane-modified polyether sealant according to claim 9, characterized in that, The concentration of the cyclodextrin polyether polyol in the aqueous solution is 0.1 g / ml to 0.15 g / ml.

11. The long-lasting antifungal silane-modified polyether sealant according to claim 9, characterized in that, The concentration of the natural antifungal agent in the alcohol solution is 0.05 g / ml to 0.07 g / ml.

12. The long-lasting antifungal silane-modified polyether sealant according to any one of claims 1-4, characterized in that, The MS-polymer prepolymer is a trimethoxysilyl-terminated polyether and / or a triethoxysilyl-terminated polyether; and / or, The reinforcing filler is at least one of nano-calcium carbonate, activated calcium carbonate, and fumed silica; and / or, The thixotropic agent is at least one of hydrogenated castor oil and polyamide wax; and / or, The plasticizer is at least one selected from diisodecyl phthalate, diisononyl phthalate, and diisooctyl phthalate; and / or, The hydroxyl scavenger is at least one of vinyltrimethoxysilane and hexamethyldisilazane; and / or, The coupling agent is at least one selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane; and / or, The organotin catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, and tin octoate.

13. A method for preparing a long-lasting antifungal silane-modified polyether sealant according to any one of claims 1-12, characterized in that, Includes the following steps: The MS-polymer prepolymer, cyclodextrin polyether polyol inclusion complex, reinforcing filler, thixotropic agent, and plasticizer are dehydrated and blended for 60 to 180 minutes at a temperature of 70℃-130℃ and a vacuum of -0.08MPa to -0.1MPa. After cooling, the hydroxyl scavenger, coupling agent, and organotin catalyst are added, and the mixture is mixed and reacted for 30 to 90 minutes at a vacuum of -0.08MPa to -0.1MPa and a stirring speed of 10Hz to 20Hz to obtain the long-lasting antifungal silane-modified polyether sealant.

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