A kind of synthesis method of acrylate modified silicone resin and its application

Abstract

The invention provides a method for synthesizing an acrylate-modified silicone resin, comprising the following steps: S1, blending graphene oxide and KH570, heating and reacting under the protection of an inert gas, then adding dibenzoyl peroxide and methacryloyloxypropyl double-terminated polydimethylsiloxane, continuing the heating and reacting, purifying, and drying to obtain modified graphene oxide; S2, blending acrylate, a functional monomer, an initiator, a stabilizer, and a solvent, heating and reacting under the protection of an inert gas, then adding the modified graphene oxide and an organosilicon monomer containing an unsaturated double bond, continuing the heating and reacting, purifying, and drying to obtain the acrylate-modified silicone resin. The acrylate-modified silicone resin of the invention has good acid and alkali resistance and weather resistance, and also has good adhesion, water resistance, and salt spray resistance, overcomes the defects existing in existing products, and has good application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of silicone resins, and in particular to a synthesis method of an acrylate-modified silicone resin and application thereof. Background Art

[0002] Silicone resins are popular in coatings, sealants, adhesives and composites due to their excellent heat resistance, electrical insulation, weather resistance and low surface energy. However, with the rapid development of technology, the application areas of silicone resins are constantly expanding, and the requirements for their performance are also increasing. Especially in acidic, alkaline or long-term exposure to harsh weather conditions, unmodified silicone resins may experience performance degradation, such as yellowing, powdering or decreased mechanical properties, which limits their application in more harsh environments.

[0003] In the prior art, in order to improve the acid and alkali resistance and weather resistance of silicone resins, researchers have tried a variety of methods, including adding acid and alkali resistant additives, using weather-resistant pigments and fillers, and enhancing the acid and alkali resistance and weather resistance of resins through chemical modification. However, these methods often only provide limited improvements and may introduce new defects, such as increasing costs, reducing processing performance, or affecting the transparency and aesthetics of the resin. In addition, silicone resins may also face problems of insufficient adhesion, water resistance, and salt spray resistance in practical applications. Insufficient adhesion may result in a weak bond between the coating or adhesive and the substrate, while insufficient water resistance and salt spray resistance may cause the material to perform poorly in a humid or salt spray environment. These problems are particularly prominent in high-performance application areas, such as the exposed surfaces of large buildings such as office buildings, airports, or high-speed rail stations, which have more stringent requirements on the acid and alkali resistance, weather resistance, adhesion, water resistance, and salt spray resistance of materials. In these areas, the existing performance of silicone resins often cannot meet the needs of long-term stability and reliability. Therefore, developing a new type of modified silicone resin to improve its acid and alkali resistance and weather resistance while maintaining or improving other physical and chemical properties has become an important research direction in the field of materials science.

[0004] In summary, it is urgent to develop a new technical solution to solve the problems existing in the prior art. Summary of the invention

[0005] The method for synthesizing an acrylate-modified silicone resin provided by the present invention adopts acrylate and an unsaturated double-bond-containing silicone monomer as main components, and simultaneously adds a functional monomer and modified graphene oxide. The prepared modified silicone resin has good acid and alkali resistance and weather resistance, as well as good adhesion, water resistance and salt spray resistance, and overcomes the defects existing in existing products.

[0006] An object of the present invention is to provide a method for synthesizing an acrylate-modified silicone resin, the method comprising the following steps:

[0007] S1, mixing graphene oxide and KH570, heating and reacting under the protection of inert gas, then adding dibenzoyl peroxide and methacryloxypropyl double-terminated polydimethylsiloxane, continuing heating and reacting, purifying and drying to obtain modified graphene oxide;

[0008] S2, blending acrylate, functional monomer, initiator, stabilizer and solvent, heating and reacting under the protection of inert gas, then adding the modified graphene oxide and the organosilicon monomer containing unsaturated double bonds, continuing the heating and reacting, purifying and drying to obtain the acrylate-modified organosilicon resin.

[0009] Furthermore, in step S1, the mass ratio of graphene oxide, KH570 and methacryloxypropyl di-terminated polydimethylsiloxane is 1:(10-30):(10-30).

[0010] Furthermore, in step S2, the mass ratio of modified graphene oxide, acrylate, functional monomer, silicone monomer containing unsaturated double bonds, initiator, stabilizer and solvent is (1-10):(10-50):(1-10):(50-100):(1-5):(1-10):(100-500).

[0011] Furthermore, the acrylic acid ester is selected from one or more of methyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate or tert-butyl acrylate.

[0012] Furthermore, the functional monomer is trimethylolpropane trimethacrylate.

[0013] Furthermore, the organic silicon monomer containing unsaturated double bonds is selected from one or more of vinyl trimethyl silane, vinyl triethoxy silane or 3-methacryloxypropyl trimethoxy silane.

[0014] Furthermore, the initiator is selected from one or more of dibenzoyl peroxide and azobisisobutyronitrile.

[0015] Furthermore, the stabilizer is polyvinyl pyrrolidone.

[0016] Furthermore, the solvent is selected from one or more of methanol, acetonitrile, ethyl acetate, propanol, acetone or n-butanol.

[0017] Furthermore, in step S1, the heating reaction temperature is 90-120°C and the time is 3-24h.

[0018] Furthermore, in step S2, the heating reaction temperature is 60-80°C and the time is 12-24h.

[0019] The present invention has the following beneficial effects:

[0020] (1) The synthesis method of the acrylate-modified silicone resin provided by the present invention adopts acrylate and silicone monomer containing unsaturated double bonds as the main components, and functional monomers and modified graphene oxide are added at the same time. The silicone resin modified by acrylate has better adhesion, stability and weather resistance; and the present invention also adds a specific functional monomer as a modifier. The functional monomer has more unsaturated double bonds and more active sites. After cross-linking and combining with other components, it can form a more stable structure, further improving the adhesion, acid and alkali resistance, salt spray resistance and weather resistance of the modified silicone resin.

[0021] (2) The present invention adopts a dispersion polymerization method, firstly copolymerizing an acrylate monomer and a functional monomer to form a core structure, and then adding modified graphene oxide and an organosilicon monomer containing unsaturated double bonds. Since the surface of the core structure has free radicals, which provide active sites, under the action of an initiator, the added modified graphene oxide and the organosilicon monomer containing unsaturated double bonds can undergo free radical polymerization on the surface of the core structure, thereby forming a shell layer, and finally forming a modified organosilicon resin with a core-shell structure. The structure has multiple buffering effects and is not easily affected by the outside world, thereby improving the acid and alkali resistance, salt spray resistance and weather resistance of the modified organosilicon resin.

[0022] (3) Graphene oxide is a nanomaterial with good chemical stability. The present invention first modifies it with KH570 to enhance its compatibility with organic materials, and then reacts with methacryloxypropyl dicapped polydimethylsiloxane to graft methacryloxypropyl dicapped polydimethylsiloxane onto graphene oxide, introduces a siloxane segment containing a double bond, and obtains modified graphene oxide. The modified graphene oxide has good compatibility with silicone resin, and when added to silicone resin, it can effectively improve the acid and alkali resistance and salt spray resistance of the modified silicone resin; in addition, the graphene oxide also has a flaky structure, which can play a physical barrier role, prevent the penetration of moisture or ultraviolet rays, and improve the water resistance and weather resistance of the modified silicone resin. DETAILED DESCRIPTION

[0023] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0024] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0025] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0026] The present invention uses the following raw materials:

[0027] The graphene oxide in the examples and comparative examples of the present invention is S28018, which was purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0028] The methacryloxypropyl di-terminated polydimethylsiloxane in the examples and comparative examples of the present invention has a molecular weight of 8000-12000 and is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0029] The polyvinyl pyrrolidone in the examples and comparative examples of the present invention has an average molecular weight of 8000 and is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0030] The film-forming material polyurethane emulsion Lacper 4219 of the test example of the present invention was purchased from Wanhua Chemical.

[0031] The defoamer Tego-805 used in the test example of the present invention was purchased from Evonik Industries.

[0032] The substrate wetting agent Byk-346 of the test example of the present invention was purchased from Shenzhen Longdi Chemical.

[0033] The leveling agent Tego-410 used in the test example of the present invention was purchased from Evonik Industries.

[0034] The thickener U604 used in the test example of the present invention was purchased from Wanhua Chemical.

[0035] The water-based color paste of the test example of the present invention was purchased from Caizhihong.

[0036] The "parts" in the embodiments of the present invention refer to parts by mass.

[0037] Example 1

[0038] A method for synthesizing an acrylate-modified silicone resin comprises the following steps:

[0039] S1. Take 20 parts of anhydrous ethanol, add 0.2 parts of graphene oxide, ultrasonicate for 60 minutes, then add 3 parts of KH570, reflux for 12 hours at 110°C under nitrogen protection; then add 0.1 parts of dibenzoyl peroxide and 3 parts of methacryloyloxypropyl di-terminated polydimethylsiloxane, reflux for 4 hours at 120°C, wash and dry to obtain modified graphene oxide;

[0040] S2. 30 parts of methyl methacrylate, 5 parts of trimethylolpropane trimethacrylate, 1 part of dibenzoyl peroxide, 5 parts of polyvinyl pyrrolidone and 300 parts of methanol are mixed, and heated to react at 80°C for 12 hours under nitrogen protection; then 7 parts of the modified graphene oxide and 80 parts of vinyltrimethylsilane are added, and the mixture is heated to react at 80°C for 12 hours, filtered and dried to obtain the acrylate-modified silicone resin.

[0041] Example 2

[0042] A method for synthesizing an acrylate-modified silicone resin comprises the following steps:

[0043] S1. Take 20 parts of anhydrous ethanol, add 0.2 parts of graphene oxide, ultrasonicate for 60 minutes, then add 3 parts of KH570, reflux for 12 hours at 110°C under nitrogen protection; then add 0.1 parts of dibenzoyl peroxide and 3 parts of methacryloyloxypropyl di-terminated polydimethylsiloxane, reflux for 4 hours at 120°C, wash and dry to obtain modified graphene oxide;

[0044] S2. 35 parts of ethyl acrylate, 6 parts of trimethylolpropane trimethacrylate, 1 part of dibenzoyl peroxide, 5 parts of polyvinyl pyrrolidone and 300 parts of methanol are mixed, and heated to react at 80°C for 12 hours under nitrogen protection; then 8 parts of the modified graphene oxide and 90 parts of vinyltrimethylsilane are added, and the mixture is heated to react at 80°C for 12 hours, filtered and dried to obtain the acrylate-modified silicone resin.

[0045] Example 3

[0046] A method for synthesizing an acrylate-modified silicone resin comprises the following steps:

[0047] S1. Take 20 parts of anhydrous ethanol, add 0.2 parts of graphene oxide, ultrasonicate for 60 minutes, then add 3 parts of KH570, reflux for 12 hours at 110°C under nitrogen protection; then add 0.1 parts of dibenzoyl peroxide and 3 parts of methacryloyloxypropyl di-terminated polydimethylsiloxane, reflux for 4 hours at 120°C, wash and dry to obtain modified graphene oxide;

[0048] S2. 40 parts of butyl acrylate, 8 parts of trimethylolpropane trimethacrylate, 1 part of dibenzoyl peroxide, 5 parts of polyvinyl pyrrolidone and 300 parts of methanol are mixed, and heated to react at 80°C for 12 hours under nitrogen protection; then 10 parts of the modified graphene oxide and 95 parts of 3-methacryloxypropyltrimethoxysilane are added, and the mixture is heated to react at 80°C for 12 hours, filtered and dried to obtain the acrylate-modified silicone resin.

[0049] Comparative Example 1

[0050] A method for synthesizing an acrylate-modified silicone resin. The difference between this comparative example and Example 1 is that step S2 is modified as follows: 30 parts of methyl methacrylate, 5 parts of trimethylolpropane trimethacrylate, 1 part of dibenzoyl peroxide, 5 parts of polyvinyl pyrrolidone, 7 parts of modified graphene oxide, 80 parts of vinyltrimethylsilane and 300 parts of methanol are mixed, heated for reaction at 80° C. for 12 hours under nitrogen protection, filtered and dried to obtain the acrylate-modified silicone resin.

[0051] Comparative Example 2

[0052] A method for synthesizing an acrylate-modified silicone resin. The difference between this comparative example and Example 1 is that step S1 is modified as follows: taking 20 parts of anhydrous ethanol, adding 0.2 parts of graphene oxide, ultrasonicating for 60 minutes, then adding 3 parts of KH570, reflux reacting for 12 hours under nitrogen protection at 110° C., washing, and drying to obtain modified graphene oxide. The amounts of other components and the preparation method are the same as those in Example 1.

[0053] Test Case

[0054] Take 30 parts of the modified silicone resin prepared in Examples 1-3 and Comparative Examples 1-2, respectively, and blend with 50 parts of polyurethane emulsion (Lacper 4219), 2 parts of dipropylene glycol methyl ether, 2 parts of dipropylene glycol butyl ether, 0.3 parts of Tego-805, 0.4 parts of Byk-346, 0.5 parts of Tego-410, 1 part of ammonia water, 0.8 parts of U604, 2 parts of aqueous color paste and 20 parts of deionized water, stir evenly, pass through a 100-mesh filter to obtain a coating, and then perform a performance test.

[0055] Test method:

[0056] Adhesion: GB / T 9286-1998; Acid and alkali resistance: GB / T 9274-1988; Water resistance: GB / T 1733-1993; Salt spray resistance: GB / T 1771-1991; Weather resistance: GB / T 1865-2009.

[0057] The test results are shown in Table 1.

[0058] Table 1 Comparison of performance test results of samples of Examples 1-3 and Comparative Examples 1-3

[0059]

[0060] From the above experimental data, it can be seen that the film-forming samples added with the acrylate-modified silicone resin prepared in Examples 1-3 have an adhesion of level 0; good acid and alkali resistance, water resistance and salt spray resistance; after 3000h of artificial aging test, the coating film does not bubble, crack or discolor. However, in Comparative Example 1, all monomers are directly copolymerized, and no core-shell structure is formed compared with Example 1; Comparative Example 2 uses KH570-grafted graphene oxide to replace modified graphene oxide, and its compatibility with silicone resin is poorer than modified graphene oxide; therefore, the performance improvement of both silicone resins is lower than that of Examples 1-3 to varying degrees. Experiments show that the silicone resin prepared by using acrylate and silicone monomers containing unsaturated double bonds as the main components, and adding functional monomers and modified graphene oxide at the same time has good acid and alkali resistance and weather resistance, as well as good adhesion, water resistance and salt spray resistance. The coating based on this resin is applied to the exposed surfaces of large buildings such as office buildings, airports or high-speed railway stations, and has good application prospects.

[0061] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0062] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for synthesizing an acrylate-modified silicone resin, characterized in that: The synthesis method of the acrylate-modified silicone resin comprises the following steps: S1, mixing graphene oxide and KH570, heating and reacting under the protection of inert gas, then adding dibenzoyl peroxide and methacryloxypropyl double-terminated polydimethylsiloxane, continuing heating and reacting, purifying and drying to obtain modified graphene oxide; S2, blending acrylate, functional monomer, initiator, stabilizer and solvent, heating and reacting under the protection of inert gas, then adding the modified graphene oxide and the organosilicon monomer containing unsaturated double bonds, continuing the heating and reacting, purifying and drying to obtain the acrylate-modified organosilicon resin; The functional monomer is trimethylolpropane trimethacrylate; The stabilizer is polyvinyl pyrrolidone; The solvent is selected from one or more of methanol, acetonitrile, ethyl acetate, propanol, acetone or n-butanol.

2. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: In step S1, the mass ratio of graphene oxide, KH570 and methacryloxypropyl di-terminated polydimethylsiloxane is 1:(10-30):(10-30).

3. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: In step S2, the mass ratio of modified graphene oxide, acrylate, functional monomer, silicone monomer containing unsaturated double bonds, initiator, stabilizer and solvent is (1-10):(10-50):(1-10):(50-100):(1-5):(1-10):(100-500).

4. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: The acrylic acid ester is selected from one or more of methyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate or tert-butyl acrylate.

5. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: The organic silicon monomer containing unsaturated double bonds is selected from one or more of vinyl trimethyl silane, vinyl triethoxy silane or 3-methacryloxypropyl trimethoxy silane.

6. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: The initiator is selected from one or more of dibenzoyl peroxide and azobisisobutyronitrile.

7. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: In step S1, the heating reaction temperature is 90-120°C and the time is 3-24 h.

8. The method for synthesizing the acrylate-modified silicone resin according to claim 1, characterized in that: In step S2, the heating reaction temperature is 60-80°C and the time is 12-24 hours.

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