Synthesis method and application of high-strength tear-resistant organosilicon polymer

Abstract

The invention relates to a synthesis method and application of a high-strength tear-resistant organosilicon polymer, and the synthesis method comprises the following steps: S1, mixing and heating carbon nanotubes, epoxy resin and a catalyst for reaction, then adding ethanolamine and propylene glycol monomethyl ether, and under the protection of inert gas, heating for reaction to obtain an intermediate product; and S2, mixing the intermediate product with amino silicon oil, carrying out a heating reaction, adding epoxy polyether, and continuing the reaction to obtain the high-strength tear-resistant organosilicon polymer. The organosilicon polymer prepared by the invention not only has good mechanical properties and excellent tear resistance, but also has good compatibility with epoxy resin and silicone rubber, can effectively improve various properties of the coating, and overcomes the problem that the properties of current like products are not ideal enough.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a synthesis method of a high-strength tear-resistant organic silicon polymer and application thereof. Background Art

[0002] Silicone materials are polymer materials with repeated siloxy groups as the main chain and alkyl groups as the side chains in their molecular structure. Silicone materials have the performance advantages of both inorganic and organic materials. They can not only remain stable in a wide range of temperature and humidity, but also have the advantages of good water resistance, flexibility, elasticity, insulation and biocompatibility. Therefore, silicone materials are widely used in many fields such as vehicles, chemicals, medical treatment, construction and electronics.

[0003] However, silicone materials also have certain defects. For example, when silicone resins are used in coatings, the stability and durability of such products in oil solvents, acid and alkali solutions and steam environments, as well as their mechanical properties such as tensile and tear strength, have major defects and have not yet reached the ideal level, limiting the use of silicone coatings in specific application scenarios. Therefore, how to improve the comprehensive performance of silicone polymers in complex and changeable industrial or outdoor environments to meet higher standards of protection requirements is an urgent issue facing this field.

[0004] The existing technology usually performs certain physical or chemical modifications on traditional silicone rubber materials to improve the various properties of such materials. For example, fillers such as silica and alumina are added to improve the strength and hardness of silicone rubber; special groups such as phenyl are introduced into the side chains of silicone rubber to avoid oxidation and degradation of the material and improve high and low temperature resistance. However, directly mixing fillers such as silica with silicone rubber will cause problems such as poor compatibility between organic resin and inorganic filler, poor dispersion and bonding between components, and insufficient performance improvement; chemical modification of silicone also has the defects of complex preparation process, high cost, and unsatisfactory improvement in mechanical properties, which makes it difficult to meet the actual needs of the market and customers.

[0005] In summary, it is urgent to develop a new technical solution to solve the problems existing in the prior art. Summary of the invention

[0006] Based on this, the present invention provides a method for synthesizing a high-strength tear-resistant organosilicon polymer and its application. In the present invention, carbon nanotubes are mixed with epoxy resin, ethanolamine and other substances to introduce amino-epoxy polyether groups, and then further reacted with amino silicone oil and epoxy polyether to introduce siloxane and alkoxy segments. The obtained organosilicon polymer not only has good mechanical properties and excellent tear resistance, but also has good compatibility with epoxy resin, silicone rubber and polyetheramine materials, and can effectively improve various properties of coatings, overcoming the problem that the performance of current similar products is not ideal.

[0007] An object of the present invention is to provide a method for synthesizing a high-strength tear-resistant organosilicon polymer, the method comprising the following steps:

[0008] S1, mixing carbon nanotubes, epoxy resin and catalyst and heating them for reaction, then adding ethanolamine and propylene glycol methyl ether, and heating them under the protection of inert gas to obtain an intermediate product;

[0009] S2. Mixing the intermediate product and amino silicone oil, heating for reaction, adding epoxy polyether, and continuing the reaction to obtain a high-strength tear-resistant silicone polymer.

[0010] Furthermore, it also includes:

[0011] S3, mixing the high-strength tear-resistant organic silicon polymer, epoxy resin, fluorine-containing resin, polyether amine, silicone rubber, additives and solvent to obtain a product.

[0012] Furthermore, the carbon nanotubes are pretreated by carboxylation.

[0013] Furthermore, in step S1, the temperature of the heating reaction is 80-90°C; the temperature of the temperature-raising reaction is 120-150°C.

[0014] Furthermore, the mass ratio of the carbon nanotubes, epoxy resin, ethanolamine and propylene glycol methyl ether is 1:(20-50):(5-10):(30-80).

[0015] Furthermore, in step S2, the temperature of the heating reaction is 120-160°C, and the temperature of the continued reaction is 70-90°C.

[0016] Furthermore, the mass ratio of the intermediate product to the amino silicone oil is 1:(0.1-2).

[0017] Furthermore, the molar ratio of the amino silicone oil to the epoxy polyether is 1:(0.1-3).

[0018] Furthermore, the auxiliary agent is selected from one or more of a dispersant, a defoamer, a leveling agent, an emulsifier, a thickener, a curing agent, a cross-linking agent, a film former, an antioxidant, a toughening agent, a catalyst and an initiator.

[0019] Furthermore, the mass ratio of the high-strength tear-resistant silicone polymer, epoxy resin, fluorine-containing resin, polyetheramine, silicone rubber and additives is (30-60):(20-40):(20-50):(20-50):(20-50):(10-20).

[0020] Another object of the present invention is to provide application of the high-strength tear-resistant organosilicon polymer in coatings.

[0021] The present invention has the following beneficial effects:

[0022] The synthesis method of the high-strength tear-resistant organic silicon polymer provided by the present invention comprises the following steps: firstly, reacting carboxylated carbon nanotubes with epoxy resin to introduce epoxy functional groups on the surface of the material; then, reacting the carbon nanotubes with ethanolamine and propylene glycol methyl ether to coat the surface of the carbon nanotubes with amino epoxy polyether macromolecules, thereby making the carbon nanotubes have a more regular surface; and introducing a chain segment containing a large number of epoxy groups, phenyl groups and ether bonds; then, heating the carbon nanotubes with amino silicone oil to introduce polysiloxane molecular chains and amino groups; and finally, reacting the amino groups with epoxy polyether to graft the alkoxy chain segments on the surface of the polymer. The obtained polymer not only has It has the excellent mechanical properties of carbon nanotubes and the characteristics of polyether, silicone and other materials. It enhances the compatibility with silicone, epoxy resin, polyetheramine and other materials while improving various properties. The dispersion effect is more uniform, which is conducive to improving the stability of coating products. In addition, the various active groups introduced into the polymer can form physical and chemical crosslinks with epoxy resin, silicone rubber, polyetheramine and other components, so that the coating has a more three-dimensional and stable network crosslinking structure. While reducing the content of epoxy resin, it further improves the mechanical properties of the product such as tear resistance and better adhesion, weather resistance and stability. In summary, the present invention solves the deficiencies in the prior art, improves the various properties of silicone polymers, and has good application prospects. 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 method for preparing carboxylated carbon nanotubes in the embodiment of the present invention comprises the following steps:

[0027] The carbon nanotubes were immersed in nitric acid with a mass concentration of 60%, ultrasonically dispersed for 0.5 h, then refluxed at 120° C. for 24 h, and then filtered, washed, and dried to obtain carboxylated carbon nanotubes.

[0028] The epoxy resin in the embodiment of the present invention is E-51 epoxy resin.

[0029] The amino silicone oil in the embodiment of the present invention is OFX-8040A.

[0030] The epoxy polyether in the embodiment of the present invention is purchased from Gaocheng Xinxing Chemical, with an epoxy value of ≥3 mmol / g, and n=3-6.

[0031] The fluorine-containing resin in the embodiment of the present invention is LF-710F emulsion; the polyetheramine is Huntsman D-230 and T-5000 in a mass ratio of 4:1; the silicone rubber is 107 silicone rubber; the additives are emulsifier AEO-9, crosslinking agent tetraethyl orthosilicate, curing agent E-100, catalyst dibutyltin dilaurate, and initiator AIBN in a mass ratio of 1:5:2:1.5:0.5.

[0032] The "parts" in the embodiments of the present invention refer to parts by mass.

[0033] Example 1

[0034] A method for synthesizing a high-strength tear-resistant silicone polymer comprises the following steps:

[0035] S1, mixing carboxylated carbon nanotubes, epoxy resin and triphenylphosphine in a mass ratio of 1:40:0.1, and ultrasonically treating for 2 hours;

[0036] Then, the mixture was reacted at 85°C for 24 h, and then ethanolamine and propylene glycol methyl ether were added in a mass ratio of 1:4.8 (carboxylated carbon nanotubes: ethanolamine = 1:8, m / m), and the mixture was reacted at 140°C for 3 h under nitrogen protection;

[0037] Then, add propylene glycol methyl ether of the same mass as that in the previous step, react at 140°C for 3 hours, extract, wash with propylene glycol methyl ether, and dry to obtain an intermediate product;

[0038] S2, mixing the intermediate product and amino silicone oil in a mass ratio of 4:1, stirring for 2 hours, then reacting at 150°C for 3 hours, filtering, washing, and drying, blending with epoxy polyether (epoxy polyether: amino silicone oil = 0.5:1, n / n), using isopropanol as solvent, reacting at 80°C for 4 hours, filtering, washing, and drying to obtain a high-strength tear-resistant silicone polymer;

[0039] S3, mixing 30 parts of the high-strength tear-resistant organic silicon polymer, 25 parts of epoxy resin, 20 parts of fluorine-containing resin, 25 parts of polyether amine, 20 parts of silicone rubber, 10 parts of additives and 6 parts of water to obtain a product.

[0040] Example 2

[0041] S1, mixing carboxylated carbon nanotubes, epoxy resin and triphenylphosphine in a mass ratio of 1:40:0.1, and ultrasonically treating for 2 hours;

[0042] Then, the mixture was reacted at 85°C for 24 h, and then ethanolamine and propylene glycol methyl ether were added in a mass ratio of 1:5 (carboxylated carbon nanotubes: ethanolamine = 1:8, m / m), and the mixture was reacted at 140°C for 3 h under nitrogen protection;

[0043] Then, add propylene glycol methyl ether of the same mass as that in the previous step, react at 140°C for 3 hours, extract, wash with propylene glycol methyl ether, and dry to obtain an intermediate product;

[0044] S2, mixing the intermediate product and amino silicone oil in a mass ratio of 4:1, stirring for 2 hours, then reacting at 150°C for 3 hours, filtering, washing, and drying, blending with epoxy polyether (epoxy polyether: amino silicone oil = 0.5:1, n / n), using isopropanol as solvent, reacting at 80°C for 4 hours, filtering, washing, and drying to obtain a high-strength tear-resistant silicone polymer;

[0045] S3, mixing 45 parts of the high-strength tear-resistant silicone polymer, 35 parts of epoxy resin, 30 parts of fluorine-containing resin, 30 parts of polyether amine, 30 parts of silicone rubber, 15 parts of additives and 10 parts of water to obtain a product.

[0046] Example 3

[0047] S1, mixing carboxylated carbon nanotubes, epoxy resin and triphenylphosphine in a mass ratio of 1:40:0.1, and ultrasonically treating for 2 hours;

[0048] Then, the mixture was reacted at 85°C for 24 h, and then ethanolamine and propylene glycol methyl ether were added in a mass ratio of 1:4.8 (carboxylated carbon nanotubes: ethanolamine = 1:8, m / m), and the mixture was reacted at 140°C for 3 h under nitrogen protection;

[0049] Then, add propylene glycol methyl ether of the same mass as that in the previous step, react at 140°C for 3 hours, extract, wash with propylene glycol methyl ether, and dry to obtain an intermediate product;

[0050] S2, mixing the intermediate product and amino silicone oil in a mass ratio of 4:1, stirring for 2 hours, then reacting at 150°C for 3 hours, filtering, washing, and drying, blending with epoxy polyether (epoxy polyether: amino silicone oil = 0.5:1, n / n), using isopropanol as solvent, reacting at 80°C for 4 hours, filtering, washing, and drying to obtain a high-strength tear-resistant silicone polymer;

[0051] S3, mixing 60 parts of the high-strength tear-resistant silicone polymer, 40 parts of epoxy resin, 40 parts of fluorine-containing resin, 40 parts of polyetheramine, 35 parts of silicone rubber, 18 parts of additives and 12 parts of water to obtain a product.

[0052] Comparative Example 1

[0053] A coating, the difference between this comparative example and application example 1 is that step S1 is modified as follows: using ethanol and water in a volume ratio of 9:1 as solvent, carbon nanotubes and epoxy silane coupling agent KH560 in a mass ratio of 2:1 are mixed, reacted at 60°C for 5h, and an intermediate product is obtained after filtering, washing and drying. The other ingredients and preparation method are the same as those in application example 1.

[0054] Comparative Example 2

[0055] A coating, the difference between this comparative example and application example 1 is: step S2 is deleted, the intermediate product and amino silicone oil in a mass ratio of 4:1 are mixed and stirred evenly to obtain a mixture, and the mixture is used to replace the high-strength tear-resistant silicone polymer with an equal mass, and the other ingredients and preparation method are the same as those in application example 1.

[0056] Test Case

[0057] The samples prepared in the embodiments and comparative examples were subjected to performance tests.

[0058] Test method: Refer to GB / T 16777 for tensile strength and tear strength tests; refer to GB / T 9286, GB / T14522 and other standards for adhesion, weather resistance and acid and alkali resistance tests.

[0059] The test results are shown in Table 1.

[0060] Table 1 Performance test results

[0061]

[0062] According to the above test results, it can be concluded that the application of the high-strength tear-resistant silicone polymer prepared by the present invention in coatings not only significantly improves the mechanical strength of the product, but also significantly improves the tensile strength and tear strength of the coating, while also having excellent adhesion, weather resistance and other properties. In Comparative Example 1, the carbon nanotubes are treated with a silane coupling agent without coating the amino-epoxy polyether segments, and in Comparative Example 2, the intermediate product is directly physically mixed with silicone oil, resulting in relatively poor compatibility of the resulting product with epoxy resin, silicone rubber and polyether amine, and it is difficult to form a stable cross-linked structure between the components, and no strong synergistic effect can be produced. Therefore, the mechanical properties, adhesion and weather resistance are not ideal.

[0063] 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.

[0064] 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 a high-strength tear-resistant silicone polymer, characterized in that: The synthesis method of the high-strength tear-resistant silicone polymer comprises the following steps: S1, mixing carbon nanotubes, epoxy resin and catalyst and heating them for reaction, then adding ethanolamine and propylene glycol methyl ether, and heating them under the protection of inert gas to obtain an intermediate product; S2. Mixing the intermediate product and amino silicone oil, heating for reaction, adding epoxy polyether, and continuing the reaction to obtain a high-strength tear-resistant silicone polymer.

2. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 1, characterized in that: Also includes: S3, mixing the high-strength tear-resistant organic silicon polymer, epoxy resin, fluorine-containing resin, polyether amine, silicone rubber, additives and solvent to obtain a product.

3. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 1, characterized in that: The carbon nanotubes are pre-treated by carboxylation.

4. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 1, characterized in that: In step S1, the temperature of the heating reaction is 80-90°C; the temperature of the temperature-raising reaction is 120-150°C.

5. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 1, characterized in that: The mass ratio of the carbon nanotubes, epoxy resin, ethanolamine and propylene glycol methyl ether is 1:(20-50):(5-10):(30-80).

6. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 1, characterized in that: In step S2, the temperature of the heating reaction is 120-160°C, and the temperature of the continued reaction is 70-90°C.

7. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 1, characterized in that: The mass ratio of the intermediate product to the amino silicone oil is 1:(0.1-2).

8. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 2, characterized in that: The auxiliary agent is selected from one or more of a dispersant, a defoamer, a leveling agent, an emulsifier, a thickener, a curing agent, a cross-linking agent, a film former, an antioxidant, a toughening agent, a catalyst and an initiator.

9. The method for synthesizing a high-strength tear-resistant silicone polymer according to claim 2, characterized in that: The mass ratio of the high-strength tear-resistant silicone polymer, epoxy resin, fluorine-containing resin, polyetheramine, silicone rubber and additives is (30-60):(20-40):(20-50):(20-50):(20-50):(10-20).

10. Use of the high-strength tear-resistant organosilicon polymer according to any one of claims 1 to 9 in coatings.

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