High-strength organic silicon modified antifouling paint resin, composition and preparation method of high-strength organic silicon modified antifouling paint resin

Abstract

The invention provides a high-strength organic silicon modified antifouling paint resin, which is a polyurethane modified organic silicon resin and comprises the following components in parts by mass: 5 to 15 parts of polyethylene glycol, 0.1 to 0.5 part of catalyst, 5 to 10 parts of diisocyanate and 25 to 45 parts of hydroxypropyl silicone oil. Compared with the traditional organic silicon resin, the resin composition prepared from the organic silicon resin has the advantages that the mechanical strength and the toughness are obviously improved after curing. When being applied to the anti-fouling paint, the anti-fouling agent can effectively enhance the mechanical property of a coating and remarkably reduce the damage risk of the coating caused by collision, so that the durability and practicability of the anti-fouling paint are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical materials, in particular to a high-strength silicone-modified antifouling coating resin, a composition and a preparation method thereof. BACKGROUND

[0002] Marine fouling refers to the phenomenon that marine organisms (such as bacteria, algae, barnacles, shellfish, etc.) adhere or deposit on the surface of underwater artificial structures such as ships, piers, buoys, and submarine pipelines, forming biological fouling. To prevent such fouling, mechanical, physical, chemical, biological or ecological means are often used for treatment. The main principles of action include killing, inhibiting growth and inhibiting adhesion, and the specific methods include artificial cleaning, external current, low surface energy coating, direct poisoning, electrolysis of seawater, chemical antifouling coating and biological antifouling. Among these methods, the application of antifouling coating is widely used because of its simple operation and long-lasting effect.

[0003] With the increasingly stringent environmental regulations, traditional toxic antifouling coatings are gradually being replaced by low-toxic or non-toxic environmentally friendly products, and the application of environmentally friendly antifouling coatings is becoming more and more widespread. Among them, the release-type antifouling coating uses silicone resin as the main film-forming material, which has good antifouling performance and environmental friendly characteristics. However, its mechanical strength is low, and the coating is easily damaged due to bumps during use, thereby affecting the protective effect and service life.

[0004] Chinese patent CN108441097A discloses a nano low surface energy antifouling coating and a preparation method. The coating includes an organic silicon polyurethane resin component and a prop component, wherein the organic silicon polyurethane resin component is obtained by reaction of a group A component and a group B component; the group A component includes isocyanate 20-40 parts, polyol 10-50 parts and polysiloxane resin 2-20 parts; the group B component includes polyol 40-60 parts, chain extender 5-20 parts and catalyst 0.1-5 parts; the prop component includes nano slurry 3-8 parts; and the curing agent is 14-18 parts. The nano low surface energy antifouling coating of the present application makes the surface protective material of the coating nanometerized, reduces the surface energy and improves the hydrophobicity, but lacks good mechanical properties, and is weak in elasticity, impact resistance and scratch resistance.

[0005] To solve the above problems, improving the mechanical properties of silicone resin has become a key direction for improving the release-type antifouling coating. It is urgent to develop a silicone-modified resin with higher strength and durability, which can significantly enhance the impact resistance and wear resistance of the coating while retaining the excellent antifouling properties and environmental friendly characteristics, thereby prolonging the service life of the coating. SUMMARY

[0006] The present invention aims to provide a high-strength organosilicon-modified antifouling coating resin, composition, and preparation method thereof. The resin composition is prepared by compounding a hydroxyl organosilicon resin with a polyurethane-modified organosilicon resin, curing with a silane coupling agent in the presence of a catalyst. Compared to traditional organosilicon resins, the resin composition prepared by the present invention exhibits significant improvements in mechanical strength and toughness. Its application in antifouling coatings can effectively enhance the mechanical properties of the coating and significantly reduce the risk of coating damage due to bumps, thereby improving the durability and practicality of the antifouling coating.

[0007] To achieve the above objectives, the present invention provides a high-strength organosilicon-modified antifouling coating resin, a composition, and a method for preparing the same. The technical solution of the present invention is achieved as follows:

[0008] A high-strength organosilicon-modified antifouling coating resin is provided. The resin is a polyurethane-modified organosilicon resin. The resin formula is 5-15 parts by weight of polyethylene glycol, 0.1-0.5 parts by weight of a catalyst, 5-10 parts by weight of a diisocyanate, and 25-45 parts by weight of a hydroxypropyl silicone oil.

[0009] Furthermore, the hydroxypropyl silicone oil is one or more of hydroxypropyl silicone oil 1000, hydroxypropyl silicone oil 2000, hydroxypropyl silicone oil 3000, and hydroxypropyl silicone oil 6000.

[0010] A high-strength organosilicon-modified antifouling coating resin composition is prepared by curing component A and component B. Component A comprises, by weight, 50-80 parts of a hydroxyl organosilicon resin, 5-20 parts of a polyurethane-modified organosilicon resin, and 20-40 parts of a solvent; component B comprises 5-8 parts of a silane coupling agent, 0.5-1 part of a catalyst, and 2-6 parts of a solvent; and the polyurethane-modified organosilicon resin comprises the above-mentioned resin.

[0011] Furthermore, the hydroxy silicone resin is a silicone resin containing hydroxyl groups at both ends.

[0012] Furthermore, the silane coupling agent is one or more of ethyl silicate, ethyl silicate 28, ethyl silicate 32, and ethyl silicate 40.

[0013] A method for preparing a high-strength organosilicon-modified antifouling coating resin composition is provided, wherein the method comprises the following steps:

[0014] S1, synthesizing the polyurethane-modified silicone resin;

[0015] S2, preparing the component A and the component B;

[0016] S3, mixing the component A and the component B in a ratio of 5:1 to 20:1, stirring evenly, and forming a film to solidify.

[0017] Furthermore, the preparation step of the component A includes: adding the hydroxy silicone resin, polyurethane-modified silicone resin and solvent into a reaction container, and dispersing them at room temperature for 5 to 30 minutes.

[0018] Furthermore, the preparation step of the component B includes: adding the silane coupling agent, catalyst and solvent into a reaction container, and dispersing them at room temperature for 5 to 30 minutes.

[0019] Furthermore, the polyurethane-modified silicone resin synthesis method comprises: adding polyethylene glycol and a catalyst to a three-necked flask, stirring and heating to 80-100° C.; adding diisocyanate dropwise to the reaction system, controlling the addition time to be 0.5-1 hour, and keeping the temperature in the reaction chamber for 0.5-2 hours after the addition is completed; adding hydroxypropyl silicone oil to the reaction system, and continuing the keeping temperature in the reaction chamber for 3-8 hours.

[0020] Furthermore, the component A and the component B are mixed in a ratio of 10:1.

[0021] Compared with the prior art, the high-strength organosilicon-modified antifouling coating resin, composition, and preparation method thereof described in the present invention have the following advantages:

[0022] After curing, the resin composition prepared by the present invention exhibits significantly improved mechanical strength and toughness compared to traditional silicone resins. Its application in the preparation of antifouling coatings can effectively enhance the coating's mechanical properties and significantly reduce the risk of coating damage caused by bumps and impacts, thereby improving the durability and practicality of the antifouling coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is an infrared spectrum of the polyurethane-modified silicone resin 1 described in Example 1 of the present invention;

[0024] Figure 2 This is a gel permeation chromatogram of the polyurethane-modified silicone resin 1 described in Example 1 of the present invention;

[0025] Figure 3 is a stress-strain curve diagram of a conventional silicone resin composition after curing;

[0026] Figure 4 This is a stress-strain curve diagram of the resin composition described in Inventive Example 1;

[0027] Figure 5 This is a stress-strain curve diagram of the resin composition described in Inventive Example 2;

[0028] Figure 6This is a graph showing three stress-strain curves of the resin composition described in Inventive Example 3;

[0029] Figure 7 This is a contact angle diagram of the resin composition after curing described in Inventive Example 1;

[0030] Figure 8 This is a structural diagram of the polyurethane-modified silicone resin described in Invention Example 1. DETAILED DESCRIPTION

[0031] To make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the embodiments described are part of the embodiments of the present invention, rather than all of the embodiments. The specific embodiments described herein are merely for explaining the present invention and are not intended to limit the present invention. It should be noted that, unless there is a conflict, the features in the embodiments and embodiments of the present invention may be combined with each other.

[0032] A high-strength organosilicon-modified antifouling coating resin is prepared by curing with two components, wherein component A comprises a hydroxy organosilicon resin, a polyurethane-modified organosilicon resin and a solvent, and component B comprises a silane coupling agent, a catalyst and a solvent.

[0033] Preferably, by mass, the formula of component A is 50-80 parts of hydroxy silicone resin, 5-20 parts of polyurethane modified silicone resin, and 20-40 parts of solvent; the formula of component B is 5-8 parts of silane coupling agent, 0.5-1 part of catalyst, and 2-6 parts of solvent.

[0034] The preparation process of component A is as follows: hydroxyl silicone resin, polyurethane-modified silicone resin and solvent are added to a reaction vessel, and high-speed dispersion is carried out at room temperature for 5 to 30 minutes. The material can be discharged after being evenly dispersed. Preferably, the dispersion time is 10 minutes.

[0035] The preparation process of component B is as follows: add silane coupling agent, catalyst and solvent to a reaction vessel, disperse at high speed at room temperature for 5 to 30 minutes, and then discharge the material after the material is evenly dispersed. Preferably, the dispersion time is 10 minutes.

[0036] When used, component A and component B are mixed in a ratio of 5:1 to 20:1, stirred evenly, and cured to form a film to obtain a high-strength organosilicon-modified antifouling coating resin composition. Preferably, the mixing ratio is 10:1.

[0037] The hydroxy silicone resin is a silicone resin containing hydroxyl groups at both ends, and its viscosity ranges from 2000 to 20000 cP.

[0038] The solvent is one or more of xylene, toluene, butyl acetate, cyclohexanone and n-butanol.

[0039] The silane coupling agent is one or more of ethyl silicate, ethyl silicate 28, ethyl silicate 32, and ethyl silicate 40.

[0040] The catalyst is one or more of dibutyltin dilaurate and stannous octoate.

[0041] Preferably, the polyurethane modified silicone resin formula is 5-15 parts of polyethylene glycol, 0.1-0.5 parts of catalyst, 5-10 parts of diisocyanate, and 25-45 parts of hydroxypropyl silicone oil, calculated by mass.

[0042] The polyethylene glycol is one or more of polyethylene glycol 200, polyethylene glycol 600, polyethylene glycol 1000, and polyethylene glycol 2000;

[0043] The catalyst is one or more of dibutyltin dilaurate and stannous octoate;

[0044] The diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, and toluene diisocyanate;

[0045] The hydroxypropyl silicone oil is one or more of hydroxypropyl silicone oil 1000, hydroxypropyl silicone oil 2000, hydroxypropyl silicone oil 3000, and hydroxypropyl silicone oil 6000.

[0046] The polyurethane modified silicone resin is synthesized by a step-by-step dropwise addition method, and the specific synthesis method is as follows:

[0047] Add polyethylene glycol and a catalyst to a three-necked flask, stir, and heat to 80-100°C. Add diisocyanate dropwise to the reaction system over a 0.5-1 hour period. After completion of the addition, incubate the reaction for 0.5-2 hours, preferably 1 hour. Add hydroxypropyl silicone oil to the reaction system, continue incubating the reaction for 3-8 hours, preferably 5 hours, and then cool and discharge the product, which is a polyurethane-modified silicone resin.

[0048] Example 1

[0049] This embodiment is to prepare a high-strength organosilicon-modified antifouling coating resin composition (resin composition 1), comprising the following steps:

[0050] S1, synthetic polyurethane modified silicone resin 1.

[0051] Add 5 parts of polyethylene glycol 200 and 0.1 parts of dibutyltin dilaurate to a three-necked flask, stir and heat to 80°C. Add 5 parts of hexamethylene diisocyanate dropwise to the reaction system over a 0.5 hour period. After the addition is complete, keep the reaction warm for 1 hour. Add 25 parts of hydroxypropyl silicone oil 1000 to the reaction system and continue to keep the reaction warm for 5 hours. Then cool and discharge the product to obtain a polyurethane-modified silicone resin. Figure 5 Schematic diagram of the structure of polyurethane modified silicone resin.

[0052] The synthesized polyurethane modified silicone resin was subjected to infrared spectroscopy analysis. Figure 1 As shown, 2200cm -1 The infrared peak of -NCO at 3300 cm has disappeared, indicating that the isocyanate has completely reacted. -1 and 1700cm -1 The characteristic absorption peaks of amino and carbonyl groups appeared at , indicating that the urethane bond was successfully formed.

[0053] The molecular weight and molecular weight distribution of the prepared polyurethane modified silicone resin were analyzed by gel permeation chromatography. Tetrahydrofuran was used as a solvent to dissolve the resin sample and prepare a 2 mg / ml solution at a flow rate of 1 ml / min and a temperature of 40°C. The gel permeation chromatogram is shown in FIG. Figure 2 The sample test peak is a single peak, indicating good resin homogeneity and a relatively complete copolymerization reaction, forming a structurally uniform polyurethane-modified silicone resin. Calculations indicate that the prepared polyurethane-modified silicone resin has a molecular weight of approximately 7200 and a narrow molecular weight distribution of approximately 1.65, indicating good controllability during the polymerization process.

[0054] S2, preparing the component A and the component B.

[0055] The preparation process of component A is as follows: add 50 parts of hydroxy silicone resin, 2000 cP, 5 parts of polyurethane modified silicone resin and 20 parts of xylene into the reaction container, disperse at high speed at room temperature for 10 minutes, and discharge the material after the material is evenly dispersed.

[0056] The preparation process of component B is as follows: add 5 parts of ethyl silicate 28, 0.5 parts of dibutyltin dilaurate and 2 parts of xylene into a reaction container, disperse at high speed at room temperature for 10 minutes, and discharge the material after the material is evenly dispersed.

[0057] S3, blending the component A and the component B in a mass ratio of 10:1, stirring evenly, applying to form a film, and curing to obtain a resin composition 1.

[0058] The contact angle of the resin composition 1 was tested using a contact angle tester. Figure 7As shown in the figure, the contact angle can reach 108°, which shows obvious hydrophobic characteristics.

[0059] The mechanical properties of the traditional silicone resin composition and the resin composition 1 were tested using a tensile testing machine. Figure 3 This is the stress-strain curve of the traditional silicone resin composition after curing, with a tensile strength of 1.31 MPa and an elongation at break of 448%. Figure 4 The stress-strain curve of the resin composition shows a tensile strength of 2.49 MPa and an elongation at break of 760%. This shows a significant improvement in both mechanical strength and toughness.

[0060] Example 2

[0061] This embodiment is to prepare a high-strength organosilicon-modified antifouling coating resin composition (resin composition 2), comprising the following steps:

[0062] S1, synthetic polyurethane modified silicone resin II.

[0063] Add 10 parts of polyethylene glycol 600 and 0.3 parts of dibutyltin dilaurate to a three-necked flask, stir and heat to 90°C. Add 7 parts of isophorone diisocyanate dropwise to the reaction system over 1 hour. After the addition is complete, keep the reaction warm for 1 hour. Then add 35 parts of hydroxypropyl silicone oil 3000 to the reaction system and continue to keep the reaction warm for 5 hours. Then cool and discharge the material. The resulting product is polyurethane modified silicone resin II.

[0064] S2, preparing the component A and the component B.

[0065] The preparation process of component A is as follows: add 60 parts of hydroxy silicone resin, 10000 cP, 10 parts of polyurethane modified silicone resin II and 30 parts of butyl acetate into the reaction container, disperse at high speed at room temperature for 10 minutes, and discharge the material after the material is evenly dispersed.

[0066] The preparation process of component B is as follows: add 7 parts of ethyl silicate 32, 0.7 parts of dibutyltin dilaurate and 4 parts of toluene into a reaction container, disperse at high speed at room temperature for 10 minutes, and discharge the material after the material is evenly dispersed.

[0067] S3, blending the component A and the component B in a mass ratio of 10:1, stirring evenly, applying to form a film, and curing to obtain a resin composition 2.

[0068] Figure 5 This is a stress-strain curve of the resin composition, with a tensile strength of 2.70 MPa and an elongation at break of 800%.

[0069] Example 3

[0070] The present embodiment is to prepare a high-strength silicone-modified antifouling coating resin composition (resin composition three), comprising the following steps:

[0071] S1, synthesis of polyurethane-modified silicone resin three.

[0072] Into a three-necked flask, 15 parts of polyethylene glycol 1000, 0.5 parts of dibutyltin dilaurate were added, and stirred to warm up to 100℃. 10 parts of toluene diisocyanate was added dropwise to the reaction system, and the dropwise time was controlled for 1 hour. After the dropwise addition was completed, the reaction was kept for 1 hour. Then 45 parts of hydroxypropyl silicone oil 6000 was added to the reaction system, and the reaction was kept for 5 hours. Then the product was cooled and discharged. The obtained product was polyurethane-modified silicone resin three.

[0073] S2, preparation of the A component and the B component.

[0074] The preparation process of the A component is as follows: 80 parts of hydroxyl silicone resin, 20000 cP, 20 parts of polyurethane-modified silicone resin three and 40 parts of cyclohexanone were added to a reaction vessel, and high-speed dispersion was carried out at room temperature for 10 minutes. After the material was uniformly dispersed, it was discharged.

[0075] The preparation process of the B component is as follows: 8 parts of ethyl silicate 40, 1 part of stannous octoate and 6 parts of dimethylbenzene were added to a reaction vessel, and high-speed dispersion was carried out at room temperature for 10 minutes. After the material was uniformly dispersed, it was discharged.

[0076] S3, the A component and the B component were blended in a mass ratio of 10:1, stirred uniformly, coated into a film, and the obtained resin after curing was resin composition three.

[0077] Figure 6 The stress-strain curve of resin composition three is shown in the following table, the tensile strength is 2.95 MPa, and the elongation at break is 917%.

[0078] The following table is the formula of high-strength silicone-modified antifouling coating resin composition of examples 1-3.

[0079]

[0080] The present application provides a high-strength silicone-modified antifouling coating resin, composition and preparation method thereof. The resin composition is prepared by compounding hydroxyl silicone resin with polyurethane-modified silicone resin, and curing by silane coupling agent under the action of catalyst. By adding polyurethane-modified silicone resin to traditional silicone resin, the mechanical strength and toughness of traditional silicone resin are greatly improved. By adjusting the ratio of soft and hard segments in polyurethane-modified silicone resin, the structure of the resin can be controlled, and the mechanical properties of the cured resin can be optimized. The resin is applied to antifouling coating, which can effectively improve the mechanical strength of antifouling coating and avoid the problem of damage to antifouling paint caused by collision of coating.

[0081] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined by the claims.

Claims

1. A high-strength organosilicon-modified antifouling coating resin, characterized in that: The resin is a polyurethane-modified silicone resin. Calculated by weight, the resin formula is 5-15 parts of polyethylene glycol, 0.1-0.5 parts of catalyst, 5-10 parts of diisocyanate, and 25-45 parts of hydroxypropyl silicone oil.

2. The resin according to claim 1, characterized in that The hydroxypropyl silicone oil is one or more of hydroxypropyl silicone oil 1000, hydroxypropyl silicone oil 2000, hydroxypropyl silicone oil 3000, and hydroxypropyl silicone oil 6000.

3. A high-strength organosilicon-modified antifouling coating resin composition, characterized in that: The resin composition is cured by component A and component B. Component A comprises 50-80 parts by mass of a hydroxy silicone resin, 5-20 parts by mass of a polyurethane-modified silicone resin, and 20-40 parts by mass of a solvent. Component B comprises 5-8 parts by mass of a silane coupling agent, 0.5-1 parts by mass of a catalyst, and 2-6 parts by mass of a solvent. The polyurethane-modified silicone resin comprises the resin described in claim 1 or 2.

4. The resin composition according to claim 3, characterized in that The hydroxy silicone resin is a silicone resin containing hydroxyl groups at both ends.

5. The resin composition according to claim 3, characterized in that The silane coupling agent is one or more of ethyl silicate, ethyl silicate 28, ethyl silicate 32, and ethyl silicate 40.

6. A method for preparing a high-strength organosilicon-modified antifouling coating resin composition, characterized in that: For preparing the high-strength organosilicon-modified antifouling coating resin composition according to any one of claims 3 to 5, the preparation method comprises the following steps: S1, synthesizing the polyurethane-modified silicone resin; S2, preparing the component A and the component B; S3, mixing the component A and the component B in a ratio of 5:1 to 20:1, stirring evenly, and forming a film to solidify.

7. The preparation method according to claim 6, characterized in that: The preparation step of the component A comprises: adding the hydroxy silicone resin, the polyurethane modified silicone resin and the solvent into a reaction container, and dispersing them at room temperature for 5 to 30 minutes.

8. The preparation method according to claim 6, characterized in that: The preparation step of the component B comprises: adding the silane coupling agent, catalyst and solvent into a reaction container, and dispersing them at room temperature for 5 to 30 minutes.

9. The preparation method according to claim 6, characterized in that: The polyurethane modified silicone resin synthesis method comprises the following steps: adding polyethylene glycol and a catalyst into a three-necked flask, stirring and heating to 80-100° C.; adding diisocyanate dropwise into the reaction system for a time of 0.5-1 hour, and then keeping the temperature for reaction for 0.5-2 hours after the addition is completed; and adding hydroxypropyl silicone oil into the reaction system, and continuing the keeping temperature for reaction for 3-8 hours.

10. The preparation method according to claim 6, characterized in that: The component A and the component B are mixed in a ratio of 10:1.

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