Water and stain repellent silicone polymers and their preparation and use

Abstract

The application provides a waterproof and antifouling polysiloxane polymer and preparation and application thereof, which comprises component A and component B, and the mass ratio of the two is 1:(0.8-1.5). In terms of mass parts, component A comprises 80-100 parts of base glue, 0.05-0.2 parts of a catalyst, 1-10 parts of a crosslinking agent; component B comprises 50-70 parts of base glue, 0.01-0.05 parts of an inhibitor, 20-40 parts of polysiloxane, 10-20 parts of a filler and 1-2 parts of an antifouling agent. The polysiloxane polymer provided by the application can effectively improve the adhesion performance while avoiding the problem of large tensile strength of the polymer, and can also make the polymer have antifouling and antibacterial properties, low toxicity and high stability, and has good application value.

Description

Technical Field

[0001] This invention relates to the field of waterproof and stain-resistant materials, and in particular to a waterproof and stain-resistant polysiloxane polymer and its preparation and application. Background Technology

[0002] Marine biofouling can damage marine engineering materials, reduce their lifespan, and cause serious economic losses and catastrophic accidents. Using waterproof and antifouling materials is a common way to solve this problem.

[0003] In recent years, with increasing attention paid to marine environmental protection, research on low-toxicity and non-toxic waterproof and antifouling materials has made some progress. Organosilicon materials are currently a hot topic in the preparation of fouling release materials, especially polysiloxane materials, which have both low surface energy and low elastic modulus, making fouling organisms easy to detach due to navigation or brushing.

[0004] Existing silicone materials are not conducive to efficient automated construction, disassembly, and repair. The long fibers of silicone materials result in significant material residue on the inner and outer walls of the enclosure, leading to substantial cleaning work. Furthermore, the hydrophobic properties of typical silicone materials are unstable, making them prone to detachment or damage, and thus unable to meet the waterproofing requirements of some components. Therefore, this application addresses these issues by providing a waterproof and anti-fouling polysiloxane polymer, while still satisfying the adhesion, waterproofing, and anti-fouling properties of silicone materials. Summary of the Invention

[0005] To address the existing technical problems, the present invention aims to provide a waterproof and stain-resistant polysiloxane polymer, its preparation, and its application. The polysiloxane polymer provided by this invention effectively improves adhesion performance while avoiding the problem of high polymer tensile strength. Furthermore, it endows the polymer with antifouling and antibacterial properties, low toxicity, and high stability, thus possessing significant application value.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention provides a waterproof and stain-resistant polysiloxane polymer, comprising component A and component B in a mass ratio of 1:(0.8-1.2). By mass, component A comprises 80-100 parts of base adhesive, 0.05-0.2 parts of catalyst, and 1-10 parts of crosslinking agent; component B comprises 50-70 parts of base adhesive, 0.01-0.05 parts of inhibitor, 20-40 parts of polysiloxane, 10-20 parts of filler, and 1-2 parts of stain repellent.

[0008] The reaction mechanism and function of this invention are as follows:

[0009] 1. The base adhesive selected in this invention is polyethylene silicone oil. Compared with monoethylene silicone oil, polyethylene silicone oil has stronger reactivity, better compatibility with organic materials, and is easy to combine with other organic materials, thereby improving process efficiency and effectively improving the performance of polysiloxane polymers. Simultaneously, the prepared crosslinking agent's silanol bonds can react with the vinyl groups in the polyethylene silicone oil, improving the polymer's elongation at break and enhancing its toughness.

[0010] Furthermore, this invention selects and adjusts two types of polyethylene silicone oils with different viscosities to enable the polysiloxane polymer to have a better elongation at break while meeting the adhesion performance requirements, effectively improving the fiber drawing of the polysiloxane polymer, facilitating cleaning during subsequent disassembly and repair, and improving work efficiency.

[0011] 2. The catalyst selected in this invention is a vinyl platinum complex, which is a complex of chloroplatinic acid and vinyl double-headed compounds. Compared with solvent-based catalysts (isopropanol, ethanol, etc. solutions of chloroplatinic acid), this catalyst has higher reactivity, lighter color, better storage stability, and better compatibility with organosilicon products, which is beneficial to improving the stability of polysiloxane polymers.

[0012] 3. The crosslinking agent of this invention is synthesized from high-hydrogen-content silicone oil, ethylcyclosiloxane, and hexaethyldisiloxane. The resulting crosslinking agent contains both methyl and ethyl groups, thus exhibiting better hydrophobic properties. High-hydrogen-content silicone oil has a high active hydrogen mass fraction, which may cause the crosslinking speed to be too fast, preventing the molecular chains from forming a complete and concentrated crosslinking network before they are fixed, thereby reducing tensile strength and hardness. By using high-hydrogen-content silicone oil combined with ethylcyclosiloxane and hexaethyldisiloxane to prepare a new crosslinking agent, the mass fraction of active hydrogen in the newly formed crosslinking agent is reduced, resulting in a polymer with a moderate crosslinking density. This effectively improves adhesion performance while avoiding the problem of excessive polymer tensile strength.

[0013] 4. This invention uses alkynyl alcohols as inhibitors, which have good compatibility with polysiloxanes. When added to the polymer, they serve as highly efficient inhibitors for platinum-catalyzed hydrosilylation, delaying crosslinking at room temperature after mixing the raw materials and improving the flowability of the polysiloxane polymer.

[0014] 5. This invention uses polysiloxane to improve the hydrophobicity and defoaming power of the polymer. Polysiloxane has low surface tension, high light transmittance, is non-toxic and odorless, and has good weather resistance, which is conducive to the application of the polymer in outdoor scenarios.

[0015] 6. This invention uses fumed silica as a filler to further enhance the waterproof performance of polysiloxane polymers. The addition of fumed silica synergistically enhances the hydrophobic properties of the polymer with polysiloxane, resulting in a significant increase in its contact angle. Furthermore, the selected fumed silica with a specific particle size exhibits excellent dispersibility in this system and can synergistically regulate the adhesion properties of the polysiloxane polymer with the base adhesive, polyethylene silicone oil.

[0016] 7. This invention employs copper pyrithione as an antifouling agent, which not only effectively inhibits the growth of fungi and bacteria, but also, together with fumed silica, prevents crustaceans, algae, and aquatic organisms from adhering to the hull, reducing biocorrosion and preventing the further diffusion of acidic and alkaline substances, thus achieving superior antifouling performance. Furthermore, copper pyrithione has low toxicity and high stability; its addition to polymers enhances material stability and extends shelf life.

[0017] In some embodiments, the base adhesive is composed of polyethylene silicone oil A with a viscosity of 5000–20000 mPa·s and polyethylene silicone oil B with a viscosity of 200–1000 mPa·s.

[0018] Preferably, the base adhesive is composed of divinyl-terminated polydimethylsiloxane A with a viscosity of 10000 mPa·s and divinyl-terminated polydimethylsiloxane B with a viscosity of 500 mPa·s.

[0019] In some embodiments, the mass ratio of the polyethylene silicone oil A to the polyethylene silicone oil B is (80-92):(8-20).

[0020] In some embodiments, the catalyst is a vinyl platinum complex.

[0021] In some embodiments, the preparation steps of the crosslinking agent are as follows:

[0022] (1) Place high-hydrogen silicone oil, ethyl cyclosiloxane, and end-capping agent hexaethyldisiloxane in a constant temperature water bath and stir and heat to the reaction temperature. Add catalyst, keep the reaction at the temperature, and slowly add sodium bicarbonate powder while stirring and neutralizing to obtain a mixture.

[0023] (2) Add activated carbon powder to the mixture obtained in step (1), remove the solid components by vacuum filtration, and refine by vacuum distillation at a temperature of 150-180°C to remove low-boiling substances, thereby obtaining the prepared crosslinking agent.

[0024] The crosslinking agent has the following structural formula:

[0025]

[0026] Where x = 15 to 48, y = 160 to 200, and both x and y are positive integers.

[0027] Preferably, the preparation steps of the crosslinking agent are as follows:

[0028] (1) Place 100g of raw materials high hydrogen content silicone oil, ethyl cyclosiloxane and hexaethyl disiloxane into a four-necked round bottom flask equipped with a stirrer, thermometer and reflux condenser, heat to 20-40℃ in a constant temperature water bath, add 3-4g of catalyst concentrated sulfuric acid, keep the reaction at the temperature for 6-10h, slowly add 6-8g of sodium bicarbonate powder, stir and neutralize to pH 6-8 to obtain a mixture;

[0029] (2) Add 5-10g of activated carbon powder to the mixture obtained in step (1), filter under reduced pressure to remove unreacted sodium bicarbonate powder and activated carbon, and purify under reduced pressure by distillation at 150-180℃ to remove low-boiling substances, thereby obtaining the prepared crosslinking agent.

[0030] More preferably, the mass ratio of high-hydrogen silicone oil, ethylcyclosiloxane, and hexaethyldisiloxane is (6.5-20):(75-92.5):(1-5).

[0031] In some embodiments, the inhibitor is one or more of 3,5-dimethyl-1-hexynyl-3-ol, 1-hexynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, and ethynylcyclohexanol.

[0032] In some embodiments, the polysiloxane is one or more of polydimethylsiloxane, polymethylphenylsiloxane, cyclomethylsiloxane, and aminosiloxane.

[0033] In some embodiments, the filler is fumed silica and the antifouling agent is copper pyridinethione.

[0034] Preferably, the particle size of the fumed silica is 2–16 μm.

[0035] On the other hand, the present invention provides the preparation of the waterproof and stain-resistant polysiloxane polymer, comprising the following steps:

[0036] 1. Mix 80-100 parts of base adhesive, 0.05-0.2 parts of catalyst, and 1-10 parts of crosslinking agent to obtain component A;

[0037] 2. Mix 50-70 parts of base adhesive, 0.01-0.05 parts of inhibitor, 20-40 parts of polysiloxane, 10-20 parts of filler, and 1-2 parts of antifouling agent to obtain component B;

[0038] 3. After mixing component A and component B in a certain proportion, the mixture is cured to obtain a polysiloxane polymer. Preferably, the preparation of the waterproof and stain-resistant polysiloxane polymer includes the following steps:

[0039] 1. Add 80-100 parts of base adhesive, 0.05-0.2 parts of catalyst, and 1-10 parts of crosslinking agent to a disperser and stir at a speed of 500 r / min for 20-30 min until uniformly mixed to obtain component A;

[0040] 2. Add 50-70 parts of base adhesive, 0.01-0.05 parts of inhibitor, 20-40 parts of polysiloxane, 10-20 parts of filler, and 1-2 parts of antifouling agent to a disperser and stir at a rate of 500 r / min for 20-30 min to obtain component B;

[0041] 3. Mix component A and component B in a certain proportion and cure at 25-50°C to obtain a polysiloxane polymer.

[0042] This invention also provides applications of the aforementioned waterproof and antifouling polysiloxane polymer, which can be widely used in the field of ship antifouling.

[0043] Beneficial effects:

[0044] (1) The base adhesive selected in this invention is polyethylene silicone oil of different viscosities. Its vinyl energy can react with the silicon-hydrogen bond energy in the crosslinking agent, which can make the polysiloxane polymer have better elongation at break, effectively improve the polymer drawing condition, enhance the toughness of the polymer, and facilitate cleaning during later disassembly and repair, thereby improving work efficiency.

[0045] (2) In this invention, vinyl platinum complex is used as a catalyst and alkynols are used as inhibitors to improve the reaction activity while ensuring good storage stability of the polymer.

[0046] (3) The crosslinking agent, polysiloxane and fumed silica of the present invention work together to make the prepared polysiloxane polymer more hydrophobic and have better dispersion properties.

[0047] (4) The present invention uses copper pyrithione as an antifouling agent, which works synergistically with fumed silica to inhibit the growth of fungi and bacteria, prevent biofouling from attaching to the hull plate, and thus achieve better antifouling performance. Detailed Implementation

[0048] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0049] Each polysiloxane polymer was prepared according to the proportions and preparation methods of the raw materials specified in the following examples and comparative examples.

[0050] To facilitate implementation of this invention by those skilled in the art, the manufacturers of some raw materials for the embodiments and comparative examples are described below:

[0051] High-hydrogen silicone oil: purchased from Anhui Aiyota Silicone Oil Co., Ltd., with a hydrogen content of 1.55%;

[0052] Polyethylene silicone oil A and polyethylene silicone oil B: purchased from Xuzhou Yihuiyang New Material Co., Ltd. Polyethylene silicone oil A is model 204-500, and polyethylene silicone oil B is model 204-10000.

[0053] Vinyl platinum complex: purchased from Hubei Chengfeng Chemical Co., Ltd., with a platinum content of 500 ppm to 12000 ppm;

[0054] 3,5-Dimethyl-1-hexynyl-3-ol: purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd.;

[0055] Fumed silica: purchased from Henan Tianchou Chemical Products Co., Ltd., with a particle size of 5μm;

[0056] Polydimethylsiloxane: purchased from Shandong Juneng Chemical Co., Ltd., model GB201-500;

[0057] Aminosiloxane: Purchased from Guangzhou Changhua Trading Co., Ltd., model number NX-0949;

[0058] Polymethylphenylsiloxane: Purchased from Shenzhen Jipeng Silicon Fluorine Materials Co., Ltd., model number SH-9604.

[0059] Preparation Example 1

[0060] The preparation steps of the crosslinking agent are as follows:

[0061] (1) Place 15g of high-hydrogen silicone oil, 84g of ethylcyclosiloxane and 1g of hexaethyldisiloxane into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser. Heat to 30°C in a constant temperature water bath. Add 3.5g of concentrated sulfuric acid as catalyst and keep the reaction at the temperature for 8 hours. Slowly add 7g of sodium bicarbonate powder and stir and neutralize to pH 7 to obtain a mixture.

[0062] (2) Add 7.5g of activated carbon powder to the mixture obtained in step (1), filter under reduced pressure to remove unreacted sodium bicarbonate powder and activated carbon, and refine by vacuum distillation at 160°C to remove low-boiling substances, thereby obtaining the prepared crosslinking agent.

[0063] The crosslinking agent has the following structural formula:

[0064]

[0065] In the structural formula of the obtained crosslinking agent, x = 36 and y = 182.

[0066] Other raw materials are not specified.

[0067] Example 1

[0068] A waterproof and stain-resistant polysiloxane polymer comprises component A and component B in a mass ratio of 1:1. By mass, component A comprises 90 parts of base adhesive, 0.1 parts of vinyl platinum complex, and 5 parts of crosslinking agent; component B comprises 60 parts of base adhesive, 0.02 parts of 3,5-dimethyl-1-hexynyl-3-ol, 15 parts of polydimethylsiloxane, 15 parts of aminosiloxane, 15 parts of fumed silica, and 1.5 parts of copper pyridinethione.

[0069] The base adhesive is composed of divinyl-terminated polydimethylsiloxane A with a viscosity of 10000 mPa·s and divinyl-terminated polydimethylsiloxane B with a viscosity of 500 mPa·s, with a mass ratio of 85:15.

[0070] The steps for preparing the waterproof and stain-resistant polysiloxane polymer are as follows:

[0071] 1. Add the base adhesive, vinyl platinum complex, and crosslinking agent to a disperser and stir at a rate of 500 r / min for 25 min until they are mixed evenly to obtain component A;

[0072] 2. Add the base adhesive, 3,5-dimethyl-1-hexynyl-3-ol, polydimethylsiloxane, aminosiloxane, fumed silica, and copper pyridinethione to a disperser and stir at a rate of 500 r / min for 25 min to obtain component B.

[0073] 3. Mix component A and component B in a certain proportion, degas under vacuum for 8 minutes, and then cure at 40°C to obtain a polysiloxane polymer.

[0074] Example 2

[0075] A waterproof and stain-resistant polysiloxane polymer comprises component A and component B in a mass ratio of 1:0.8. By mass, component A comprises 80 parts of base adhesive, 0.05 parts of vinyl platinum complex, and 1 part of crosslinking agent; component B comprises 50 parts of base adhesive, 0.01 parts of 3,5-dimethyl-1-hexynyl-3-ol, 10 parts of polydimethylsiloxane, 10 parts of aminosiloxane, 10 parts of fumed silica, and 1 part of copper pyridinethione.

[0076] The base adhesive is composed of divinyl-terminated polydimethylsiloxane A with a viscosity of 10000 mPa·s and divinyl-terminated polydimethylsiloxane B with a viscosity of 500 mPa·s, with a mass ratio of 85:15.

[0077] The steps for preparing the waterproof and stain-resistant polysiloxane polymer are the same as in Example 1.

[0078] Example 3

[0079] A waterproof and stain-resistant polysiloxane polymer comprises component A and component B in a mass ratio of 1:1.2. By mass, component A comprises 100 parts of base adhesive, 0.2 parts of vinyl platinum complex, and 10 parts of crosslinking agent; component B comprises 70 parts of base adhesive, 0.05 parts of 3,5-dimethyl-1-hexynyl-3-ol, 20 parts of polydimethylsiloxane, 20 parts of aminosiloxane, 20 parts of fumed silica, and 2 parts of copper pyridinethione.

[0080] The base adhesive is composed of divinyl-terminated polydimethylsiloxane A with a viscosity of 10000 mPa·s and divinyl-terminated polydimethylsiloxane B with a viscosity of 500 mPa·s, with a mass ratio of 85:15.

[0081] The steps for preparing the waterproof and stain-resistant polysiloxane polymer are the same as in Example 1.

[0082] Example 4

[0083] A waterproof and stain-resistant polysiloxane polymer, comprising the same raw materials and preparation method as in Example 1, the difference being that the base adhesive is a divinyl-terminated polydimethylsiloxane A with a viscosity of 10000 mPa·s.

[0084] Example 5

[0085] A waterproof and stain-resistant polysiloxane polymer, comprising the same raw materials and preparation method as in Example 1, the difference being that a high-hydrogen-content silicone oil is used as the crosslinking agent.

[0086] Comparative Example 1

[0087] A waterproof and stain-resistant polysiloxane polymer, comprising the same raw materials and preparation method as in Example 1, except that the base adhesive does not contain fumed silica.

[0088] Effect evaluation:

[0089] The waterproof and stain-resistant polysiloxane polymers obtained in Examples 1-5 and Comparative Example 1 were subjected to the following performance tests:

[0090] 1. Hydrophobicity

[0091] The contact angle was measured using a contact angle meter to characterize the hydrophobicity of the prepared polymer.

[0092] 2. Anti-fouling performance

[0093] The antifouling performance was tested using a diatom adhesion experiment. The specific method is as follows: 2 mL of diatom suspension was added to each well of a 24-well plate coated with a polymer. After 24 hours of adhesion, the glass plate was gently rinsed with filtered and sterilized artificial seawater to remove any unattached diatoms. The antifouling performance was evaluated by observing the plate under an optical microscope and taking three fields of view. If the average number of diatoms observed in the three fields of view was high (n ≥ 20), the antifouling performance was poor. If the average number of diatoms observed in the fields of view was low (n < 20), the antifouling performance was good. The specific results are shown in Table 1.

[0094] Table 1 Contact Angle and Antifouling Performance

[0095] Contact angle antifouling performance Example 1 125° good Example 2 115° good Example 3 128° good Example 4 117° good Example 5 105° good Comparative Example 1 98° not good

[0096] Examples 1-3 of this invention all exhibit good waterproof and stain-resistant properties, demonstrating excellent overall performance. Example 4, compared to Example 1, uses a vinyl-terminated polydimethylsiloxane A with a viscosity of 10000 mPa·s as the base adhesive. While still exhibiting good waterproof and stain-resistant properties, it reduces the elongation at break and toughness of the polysiloxane polymer, resulting in poorer overall performance. Example 5, compared to Example 1, uses a high-hydrogen-content silicone oil instead of the synthesized crosslinking agent. The lack of ethyl bonds in this oil leads to poorer waterproof performance in the resulting polymer. Comparative Example 1, compared to Example 1 which did not add fumed silica, shows a significant reduction in both hydrophobicity and stain-resistant properties.

[0097] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present application in any way. Although the present application discloses the preferred embodiment as described above, it is not intended to limit the present application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of the present application using the disclosed technical content are equivalent to equivalent implementation cases. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A waterproof and stain-resistant polysiloxane polymer, characterized in that, It includes component A and component B, with a mass ratio of 1:(0.8-1.2). By weight, component A comprises 80-100 parts of base adhesive, 0.05-0.2 parts of catalyst, and 1-10 parts of crosslinking agent; component B comprises 50-70 parts of base adhesive, 0.01-0.05 parts of inhibitor, 20-40 parts of polysiloxane, 10-20 parts of filler, and 1-2 parts of antifouling agent; wherein the base adhesive is composed of polyethylene silicone oil A with a viscosity of 10000 mPa·s and polyethylene silicone oil B with a viscosity of 500 mPa·s; The mass ratio of the polyethylene silicone oil A to the polyethylene silicone oil B is 85:15; The polysiloxane is a mixture of polydimethylsiloxane and aminosiloxane in a mass ratio of 1:1; The filler is fumed silica, and the particle size of the fumed silica is 2~16μm; The preparation steps of the crosslinking agent are as follows: (1) Place high-hydrogen silicone oil, ethyl cyclosiloxane, and end-capping agent in a constant temperature water bath and stir and heat to the reaction temperature. Add catalyst, keep the reaction at the temperature, slowly add sodium bicarbonate powder, stir and neutralize to obtain a mixture. (2) Add activated carbon powder to the mixture obtained in step (1), remove the solid components by vacuum filtration, and purify by vacuum distillation at a temperature of 150~180℃ to remove low-boiling substances, thereby obtaining the prepared crosslinking agent; wherein, the structural formula of the crosslinking agent is as follows: Where x = 15~48, y = 160~200, and x and y are both positive integers; The capping agent is hexaethyldisiloxane; The mass ratio of the high-hydrogen-content silicone oil, ethylcyclosiloxane, and hexaethyldisiloxane is (6.5-20):(75-92.5):(1-5).

2. The waterproof and stain-resistant polysiloxane polymer according to claim 1, characterized in that, The catalyst is a vinyl platinum complex.

3. The waterproof and stain-resistant polysiloxane polymer according to claim 1, characterized in that, The inhibitor is one or more of 3,5-dimethyl-1-hexynyl-3-ol, 1-hexynyl-1-cyclohexanol, 2-methyl-3-butynyl-2-ol, and ethynylcyclohexanol.

4. The waterproof and stain-resistant polysiloxane polymer according to claim 1, characterized in that, The antifouling agent is copper pyrithione.

5. A method for preparing the waterproof and stain-resistant polysiloxane polymer according to any one of claims 1-4, characterized in that, Includes the following steps:

1. Mix 80-100 parts of base adhesive, 0.05-0.2 parts of catalyst, and 1-10 parts of crosslinking agent to obtain component A; 2. Mix 50-70 parts of base adhesive, 0.01-0.05 parts of inhibitor, 20-40 parts of polysiloxane, 10-20 parts of filler, and 1-2 parts of antifouling agent to obtain component B; 3. Mix component A and component B in a certain proportion and then cure to obtain a polysiloxane polymer.

6. The application of the waterproof and stain-resistant polysiloxane polymer according to any one of claims 1-4, characterized in that, It is used in the field of ship antifouling.

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