Fluorine-containing epoxy resin, and preparation method and application thereof

Abstract

The application relates to the technical field of modified epoxy resins, in particular to a fluorine-containing epoxy resin and a preparation method and application thereof, and can solve the problem that the modification effect of a fluorine-containing epoxy resin prepared by physically blending an epoxy resin and a fluorine-containing curing agent is limited due to poor compatibility between the two. The preparation method of the fluorine-containing epoxy resin comprises the following steps: taking 2-(but-3-enyloxy)-3-hydroxypropyl acetate and maleic anhydride, performing esterification reaction under first preset conditions to obtain a first intermediate product; taking the first intermediate product and perfluoro-1-octanol, performing esterification reaction under second preset conditions to obtain a second intermediate product; and taking the second intermediate product and an oxidizing agent, performing epoxidation reaction under third preset conditions to obtain the fluorine-containing epoxy resin.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of modified epoxy resin, in particular to a fluorine-containing epoxy resin and a preparation method and application thereof. BACKGROUND

[0002] Epoxy resin has excellent thermal stability, insulation and excellent mechanical properties, and is widely used in coating, adhesive, electronic packaging material, aerospace and other fields. However, the traditional epoxy resin has the problems of poor weather resistance, wear resistance, hydrophobicity and oleophobicity, and the cured epoxy resin has the defects of brittle quality and poor surface energy, which limits the application of epoxy resin in advanced materials. Therefore, it has become a research hotspot to develop high-performance epoxy resin to meet the performance requirements in advanced materials.

[0003] The fluorine element has strong electronegativity, the C-F bond energy is large, and the interface of fluorine-containing polymer has small air molecule interaction and low surface free energy. Therefore, by introducing C-F bond to modify the epoxy resin, the weather resistance, wear resistance and hydrophobicity and oleophobicity of the epoxy resin can be improved from the molecular level by using the characteristics of C-F bond, and the application field of the epoxy resin is expanded.

[0004] In the prior art, the preparation of fluorine-containing epoxy resin is mainly physical blending of epoxy resin and fluorine-containing curing agent to introduce fluorine-containing components into the epoxy resin through the fluorine-containing curing agent. However, there is a problem of poor compatibility between the epoxy resin and the fluorine-containing curing agent in the physical blending process, which further leads to limited modification effect of the prepared fluorine-containing epoxy resin. SUMMARY

[0005] In order to solve the problem of limited modification effect of the prepared fluorine-containing epoxy resin due to the poor compatibility between the epoxy resin and the fluorine-containing curing agent in the physical blending process in the prior art, the present application provides a fluorine-containing epoxy resin and a preparation method and application thereof.

[0006] The embodiments of the present application are implemented as follows:

[0007] The present application provides a fluorine-containing epoxy resin, which is made of the following raw materials: 2-(-but-3-enyloxy)-3-hydroxypropyl acetate, maleic anhydride, perfluoro-1-octanol and an oxidizing agent.

[0008] The molar ratio of 2-(but-3-enyloxy)-3-hydroxypropyl acetate to maleic anhydride is (1.1-1.3) : 1; the molar ratio of the first intermediate product to perfluoro-1-octanol is 1:(1.1-1.3), and the molar ratio of the second intermediate product to the oxidizing agent is 1:(2.1-2.3);

[0009] The first intermediate product is prepared by reacting 2-(but-3-enyloxy)-3-hydroxypropyl acetate with maleic anhydride, and the second intermediate product is prepared by reacting the first intermediate product with the perfluoro-1-octanol.

[0010] The application also provides a preparation method of the fluorine-containing epoxy resin, which comprises:

[0011] 2-(but-3-enyloxy)-3-hydroxypropyl acetate is taken and reacted with maleic anhydride under first preset conditions to perform esterification reaction, so as to obtain a first intermediate product;

[0012] The first intermediate product and perfluoro-1-octanol are taken and reacted under second preset conditions to perform esterification reaction, so as to obtain a second intermediate product;

[0013] The second intermediate product and an oxidizing agent are taken and reacted under third preset conditions to perform epoxidation reaction, so as to obtain the fluorine-containing epoxy resin.

[0014] In some embodiments, the 2-(but-3-enyloxy)-3-hydroxypropyl acetate is taken and reacted with maleic anhydride under first preset conditions to perform esterification reaction, so as to obtain a first intermediate product, which comprises:

[0015] 2-(but-3-enyloxy)-3-hydroxypropyl acetate is taken and reacted with maleic anhydride under a temperature of 90-120°C for 3-6h to perform esterification reaction, so as to obtain the first intermediate product.

[0016] In some embodiments, the molar ratio of the 2-(but-3-enyloxy)-3-hydroxypropyl acetate to the maleic anhydride is (1.1-1.3):1.

[0017] In some embodiments, the first intermediate product and perfluoro-1-octanol are taken and reacted under second preset conditions to perform esterification reaction, so as to obtain a second intermediate product, which comprises:

[0018] The first intermediate product, perfluoro-1-octanol and concentrated sulfuric acid are mixed and reacted under a temperature of 90-120°C for 3-6h to perform esterification reaction, so as to obtain the second intermediate product.

[0019] In some embodiments, the molar ratio of the first intermediate product to the perfluoro-1-octanol is 1:(1.1-1.3), and the mass of the concentrated sulfuric acid is 2%-3% of the mass of the perfluoro-1-octanol.

[0020] In some embodiments, the second intermediate product and an oxidizing agent are taken and reacted under third preset conditions to perform epoxidation reaction, so as to obtain the fluorine-containing epoxy resin, which comprises:

[0021] The oxidizing agent is dissolved in a solvent and then slowly added into the second intermediate product, and the epoxidation reaction is carried out at a reaction temperature of 5-15℃ for 8-12h to obtain the fluorine-containing epoxy resin.

[0022] In some embodiments, the molar ratio of the second intermediate product to the oxidizing agent is 1:(2.1-2.3), the oxidizing agent is meta-chloro perbenzoic acid, and the solvent is dichloromethane.

[0023] The application also provides an application of the fluorine-containing epoxy resin, which includes the application of the fluorine-containing epoxy resin in coating, electronic packaging, adhesive, and advanced material fields.

[0024] The application has the following advantages: in the application, 2-(but-3-enyloxy)-3-hydroxypropyl acetate is first reacted with maleic anhydride to obtain a first intermediate product containing a carboxyl group, then the first intermediate product is esterified with perfluoro-1-octanol to obtain a second intermediate product containing a fluorine-containing chain, and finally the second intermediate product is subjected to epoxidation under the oxidation of an oxidizing agent to obtain a fluorine-containing epoxy resin.

[0025] The fluorine-containing epoxy resin synthesis method of the application is simple and the raw materials are easy to obtain; by adding perfluoro-1-octanol, the fluorine-containing chain segment is introduced into the epoxy resin chain segment, the fluorine content in perfluoro-1-octanol is high, and thus the fluorine content of the fluorine-containing epoxy resin is improved; meanwhile, the fluorine-containing epoxy resin prepared in the application has good compatibility between the epoxy resin chain segment and the fluorine-containing chain segment, and thus the problem of poor compatibility when the epoxy resin is physically blended with a curing agent containing a fluorine-containing chain segment is overcome; further, due to the short bond length and high bond energy of C-F bond, the introduction of C-F bond, the spiral distribution of fluorine atoms on the zigzag carbon chain, the large electronegativity of fluorine atoms, and the large repulsion between fluorine atoms, the intermolecular force of the fluorine-containing epoxy resin is small, the surface free energy is low, the surface friction coefficient of the cured fluorine-containing epoxy resin is small, and the fluorine-containing epoxy resin has excellent wear resistance; further, since the C-F bond is introduced into the fluorine-containing epoxy resin of the application, the bond energy of the C-F bond is high and the proportion of the C-F bond in the molecular chain segment is high, and thus the impact resistance and weather resistance of the coating are improved; further, since the fluorine atoms of the fluorine-containing epoxy resin are easy to enrich on the surface of the epoxy resin coating, the cured epoxy resin has strong hydrophobicity. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are some embodiments of the application, and other drawings can also be obtained by those skilled in the art without any creative labor.

[0027] Figure 1 NMR spectra of the examples of the present application. DETAILED DESCRIPTION

[0028] To enable persons skilled in the art to better understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used in the text are of the usual meaning understood by those skilled in the art of the present application, and in the event of a conflict, the definition in the specification shall prevail.

[0029] Theories and mechanisms described and disclosed herein, whether correct or not, should not be considered limiting of the scope of the present application, which is limited only by the claims. The present application can be implemented in ways other than those specifically set forth herein without departing from the spirit or scope of the present application.

[0030] In the present text, all features defined by a numerical range or a percentage range, such as numerical values, amounts, contents and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of a numerical range or a percentage range should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range, including integers and fractions.

[0031] In the present text, unless otherwise specified, "comprise", "include", "contain", "have" or similar words encompass the meaning of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meaning of "A comprises a and other" and "A comprises only a".

[0032] In the present text, for the sake of brevity of the description, all possible combinations of the various technical features in the various embodiments or examples are not described. Therefore, as long as the combinations of the technical features do not contradict each other, the various technical features in the various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered as falling within the scope of the present specification.

[0033] The present application will be further described with reference to the following specific examples. It should be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that those skilled in the art can make various modifications or changes to the present application after reading the content of the present application, and these equivalent forms also fall within the scope of the claims appended to the present application.

[0034] The following examples use apparatus and equipment that are conventional in the art. The experimental methods in the following examples, unless otherwise specified, are generally conducted under conventional conditions, or under conditions recommended by the manufacturer. The following examples use various raw materials, unless otherwise specified, and all use conventional commercially available products, which are of conventional specifications in the art. In the specification of the present application and in the following examples, unless otherwise specified, "%" means weight percent, "parts" means parts by weight, and the ratio means weight ratio.

[0035] The embodiment of the present application provides a fluorine-containing epoxy resin, which is made of the following raw materials: 2-(but-3-enyloxy)-3-hydroxypropyl acetate, maleic anhydride, perfluoro-1-octanol and an oxidizing agent.

[0036] The molar ratio of 2-(but-3-enyloxy)-3-hydroxypropyl acetate to maleic anhydride is (1.1-1.3):1; the molar ratio of the first intermediate product to perfluoro-1-octanol is 1:(1.1-1.3), and the molar ratio of the second intermediate product to the oxidizing agent is 1:(2.1-2.3);

[0037] The first intermediate product is made by the reaction of 2-(but-3-enyloxy)-3-hydroxypropyl acetate and maleic anhydride, and the second intermediate product is made by the reaction of the first intermediate product and perfluoro-1-octanol.

[0038] In the present application, first, 2-(but-3-enyloxy)-3-hydroxypropyl acetate reacts with maleic anhydride to generate a first intermediate product containing a carboxyl group, then the first intermediate product is esterified with perfluoro-1-octanol to generate a second intermediate product containing a fluorine-containing chain, and finally the second intermediate product is subjected to epoxidation under the oxidation of an oxidizing agent to generate a fluorine-containing epoxy resin.

[0039] The fluorine-containing epoxy resin synthesis method of the present application is simple, and raw materials are easy to obtain; by adding perfluoro-1-octanol, the fluorine-containing segment is introduced into the epoxy resin segment, the fluorine content of the perfluoro-1-octanol is high, and therefore the fluorine content of the fluorine-containing epoxy resin is improved; meanwhile, the fluorine-containing epoxy resin prepared by the present application has good compatibility between the epoxy resin segment and the fluorine-containing segment, and overcomes the problem of poor compatibility when the epoxy resin is physically blended with the curing agent containing the fluorine-containing segment; further, due to the short bond length and high bond energy of C-F bond, the introduction of C-F bond, the fluorine atoms are distributed in a spiral shape on the zigzag carbon chain, the shielding effect of fluorine atoms on C-C bond is enhanced, the fluorine atoms have high electronegativity, and the repulsion between fluorine atoms is large, thereby reducing the intermolecular force of the fluorine-containing epoxy resin and the surface free energy, and further reducing the surface friction coefficient of the cured fluorine-containing epoxy resin and improving the wear resistance; further, due to the introduction of C-F bond in the fluorine-containing epoxy resin of the present application, the bond energy of C-F bond is high and the proportion of C-F bond in the molecular segment is high, and the impact resistance and weather resistance of the coating are improved; further, the fluorine atoms of the fluorine-containing epoxy resin are easy to enrich on the surface of the epoxy resin coating, so that the cured epoxy resin has strong hydrophobicity.

[0040] The preparation method of the fluorine-containing epoxy resin provided by the present application comprises the following steps:

[0041] The 2-(but-3-enyloxy)-3-hydroxypropyl acetate and maleic anhydride are subjected to esterification reaction under the first preset condition to obtain the first intermediate product.

[0042] The first intermediate product and perfluoro-1-octanol are subjected to esterification reaction under the second preset condition to obtain the second intermediate product.

[0043] The second intermediate product and the oxidizing agent are subjected to epoxidation reaction under the third preset condition to obtain the fluorine-containing epoxy resin.

[0044] In some embodiments, the 2-(but-3-enyloxy)-3-hydroxypropyl acetate and maleic anhydride are subjected to esterification reaction under the first preset condition to obtain the first intermediate product, including:

[0045] The 2-(but-3-enyloxy)-3-hydroxypropyl acetate and maleic anhydride are subjected to esterification reaction at a temperature of 90-120℃ for 3-6h to obtain the first intermediate product.

[0046] In some embodiments, the molar ratio of 2-(but-3-enyloxy)-3-hydroxypropyl acetate to maleic anhydride is (1.1-1.3):1.

[0047] In some embodiments, the first intermediate product and perfluoro-1-octanol are subjected to esterification reaction under the second preset condition to obtain the second intermediate product, including:

[0048] The first intermediate product, perfluoro-1-octanol and concentrated sulfuric acid are mixed to carry out esterification reaction at a temperature of 90-120℃ for 3-6h to obtain a second intermediate product.

[0049] In some embodiments, the molar ratio of the first intermediate product to perfluoro-1-octanol is 1:(1.1-1.3), and the mass of concentrated sulfuric acid is 2%-3% of the mass of perfluoro-1-octanol.

[0050] In some embodiments, the second intermediate product and the oxidizing agent are taken to carry out epoxidation reaction under the third preset condition to obtain the fluorine-containing epoxy resin, including:

[0051] The oxidizing agent is dissolved in a solvent and then slowly added dropwise into the second intermediate product to carry out epoxidation reaction at a reaction temperature of 5-15℃ for 8-12h to obtain the fluorine-containing epoxy resin.

[0052] In some embodiments, the molar ratio of the second intermediate product to the oxidizing agent is 1:(2.1-2.3), the oxidizing agent is meta-chloro peroxide benzoic acid (i.e. mCPBA), and the solvent is dichloromethane.

[0053] In some embodiments, the principle equation for preparing the fluorine-containing epoxy resin is also provided:

[0054]

[0055] In the present application, first, 2-(but-3-enyloxy)-3-hydroxypropyl acetate reacts with maleic anhydride to generate the first intermediate product containing carboxyl, then the first intermediate product carries out esterification reaction with perfluoro-1-octanol to generate the second intermediate product containing fluorine-containing chain, and finally the second intermediate product carries out epoxidation reaction under the oxidation of the oxidizing agent to generate the fluorine-containing epoxy resin;

[0056] The fluorine-containing epoxy resin synthesis method of the present application is simple, and raw materials are easy to obtain; by adding perfluoro-1-octanol, the fluorine-containing segment is introduced into the epoxy resin segment, the fluorine content of perfluoro-1-octanol is high, and therefore the fluorine content of the fluorine-containing epoxy resin is increased, meanwhile, the fluorine-containing epoxy resin prepared by the present application has good compatibility between the epoxy resin segment and the fluorine-containing segment, and overcomes the problem of poor compatibility when the epoxy resin is physically blended with the curing agent containing the fluorine-containing segment; further, due to the short bond length and high bond energy of C-F bond, the introduction of C-F bond, the fluorine atoms are distributed in a spiral shape on the zigzag carbon chain, the shielding effect of fluorine atoms on C-C bond is enhanced, the fluorine atoms have high electronegativity, and the repulsion between fluorine atoms is large, and therefore the intermolecular force of the fluorine-containing epoxy resin is small, the surface free energy is low, and the surface friction coefficient of the cured fluorine-containing epoxy resin is small, and the fluorine-containing epoxy resin has excellent wear resistance; further, since the fluorine-containing epoxy resin of the present application introduces C-F bond, the bond energy of C-F bond is high and the proportion of C-F bond in the molecular segment is high, and the impact resistance and weather resistance of the coating are improved; further, since the fluorine atoms of the fluorine-containing epoxy resin are easy to enrich on the surface of the epoxy resin coating, the cured epoxy resin has strong hydrophobicity.

[0057] The present application also provides an application of the fluorine-containing epoxy resin, including the application of the fluorine-containing epoxy resin in the fields of coating, electronic packaging, adhesive and advanced materials. The advanced material is a 3D printing material, which is used for printing a 3D model. The application of the fluorine-containing epoxy resin in the field of advanced materials includes the application of the fluorine-containing epoxy resin as a 3D printing material.

[0058] The present application will be further described below in combination with specific examples.

[0059] Example 1

[0060] Firstly, 5g of 2-(but-3-enyloxy)-3-hydroxypropyl acetate was added into a three-necked flask equipped with a rotor, a thermometer and a reflux condenser, magnetic stirring was started, the oil bath temperature was 110℃, after preheating, 2.9g of maleic anhydride was added for a reaction of 5.5h, and a first intermediate product was obtained;

[0061] Then, 11.7g of perfluoro-1-octanol and 1mL of concentrated sulfuric acid were added into the first intermediate product for a further esterification reaction of 2h, a second intermediate product was obtained, and the second intermediate product in the three-necked flask was cooled;

[0062] Finally, the three-necked flask containing the second intermediate product cooled to room temperature was moved to an ice-water bath, 9.5g of m-chloroperoxybenzoic acid and 2.9g of dichloromethane were added when the temperature of the reaction liquid was 5℃-15℃, and an epoxidation reaction was carried out for 10h, and a fluorine-containing epoxy resin was obtained.

[0063] Example 2

[0064] First, add 8g of 2-(but-3-enyloxy)-3-hydroxypropyl acetate into a three-necked flask equipped with a rotor, a thermometer and a reflux condenser, open the magnetic stirring, the oil bath temperature is 110°C, after preheating, add 5g of maleic anhydride to react for 6h to obtain the first intermediate product;

[0065] Then, add 18.7g of perfluoro-1-octanol and 2ml of concentrated sulfuric acid into the three-necked flask to continue the esterification reaction for 2h to obtain the second intermediate product, and cool the second intermediate product in the three-necked flask;

[0066] Finally, move the three-necked flask containing the second intermediate product cooled to room temperature to an ice water bath, add 15.5g of meta-chloro peroxide benzoic acid and 4.0g of dichloromethane when the reaction liquid temperature is 5-15°C, and perform the epoxidation reaction for 10h to obtain the fluorine-containing epoxy resin.

[0067] Example 3

[0068] First, add 8g of 2-(but-3-enyloxy)-3-hydroxypropyl acetate into a three-necked flask equipped with a rotor, a thermometer and a reflux condenser, open the magnetic stirring, the oil bath temperature is 110°C, after preheating, add 5g of maleic anhydride to react for 6h to obtain the first intermediate product;

[0069] Then, add 20.4g of perfluoro-1-octanol and 2ml of concentrated sulfuric acid into the first intermediate product to continue the esterification reaction for 2h to obtain the second intermediate product, and cool the second intermediate product in the three-necked flask;

[0070] Finally, move the three-necked flask containing the second intermediate product cooled to room temperature to an ice water bath, add 16.8g of meta-chloro peroxide benzoic acid and 4.3g of dichloromethane when the reaction liquid temperature is 5-15°C, and perform the epoxidation reaction for 11h to obtain the fluorine-containing epoxy resin.

[0071] Example 4

[0072] First, add 15g of 2-(but-3-enyloxy)-3-hydroxypropyl acetate into a three-necked flask equipped with a rotor, a thermometer and a reflux condenser, open the magnetic stirring, the oil bath temperature is 110°C, after preheating, add 8.6g of maleic anhydride to react for 5h to obtain the first intermediate product;

[0073] Then, add 35.2g of perfluoro-1-octanol and 2ml of concentrated sulfuric acid into the first intermediate product to continue the esterification reaction for 2h to obtain the second intermediate product, and cool the second intermediate product in the three-necked flask;

[0074] Finally, the three-neck flask containing the second intermediate product cooled to room temperature was moved to an ice-water bath, and 29.0 g of meta-chloro peroxide benzoic acid and 7.5 g of dichloromethane were added when the temperature of the reaction liquid was 5-15°C, and the reaction was carried out for 10 h to obtain the fluorine-containing epoxy resin.

[0075] Example 5

[0076] First, 18 g of 2-(but-3-enyloxy)-3-hydroxypropyl acetate was added to a three-neck flask containing a rotor, a thermometer and a reflux condenser, the magnetic stirring was turned on, the oil bath temperature was 110°C, and after preheating, 8.6 g of maleic anhydride was added for reaction for 5 h to obtain a first intermediate product;

[0077] Then, 38.4 g of perfluoro-1-octanol and 2 ml of concentrated sulfuric acid were added to the first intermediate product for further esterification reaction for 2 h to obtain a second intermediate product, and the second intermediate product in the three-neck flask was cooled;

[0078] Finally, the three-neck flask containing the second intermediate product cooled to room temperature was moved to an ice-water bath, and 31.7 g of meta-chloro peroxide benzoic acid and 8.2 g of dichloromethane were added when the temperature of the reaction liquid was 5-15°C, and the reaction was carried out for 10 h to obtain the fluorine-containing epoxy resin.

[0079] Example 6

[0080] Preparation of a fluorine-containing epoxy resin cured waterproof coating: the fluorine-containing epoxy resin prepared according to the method described in Examples 1-5 was mixed with an epoxy curing agent, an initiator and an active diluent in a certain proportion, stirred uniformly, coated on the surface of a glass plate, and placed in a 60°C oven for curing for 20 min to obtain a fluorine-containing epoxy resin cured coating.

[0081] Characterization and testing:

[0082] In order to characterize the structural features of a fluorine-containing epoxy resin, the fluorine-containing epoxy resin synthesized in Example 6 was subjected to nuclear magnetic hydrogen spectrum test, and the nuclear magnetic hydrogen spectrum chart is shown in Figure 1 The test results are as follows:

[0083] 1 H NMR (300 MHz, DMSO): δ 4.48 (m, H), 4.38 (m, H), 4.32 (m, H), 4.07 (m, H), 2.60 (m, H), 2.44 (m, H), 2.35 (t, H), 2.04 (s, H), 1.64 (m, H) ppm.

[0084] According to the nuclear magnetic data, a fluorine-containing epoxy resin with a target structure is successfully prepared.

[0085] The performance of the cured fluorine-containing epoxy resin coating prepared from the fluorine-containing epoxy resin prepared in Examples 1-5 was measured, and the coating thickness was 1 mm. Specifically, the fluorine-containing epoxy resin prepared according to the method described in Examples 1-5 was mixed with an epoxy curing agent, an initiator and an active diluent in a certain proportion, stirred uniformly, coated on the surface of a glass plate, and placed in a 60°C oven for curing for 20 min to obtain a cured fluorine-containing epoxy resin coating.

[0086] The coating samples of the cured fluorine-containing epoxy resin coating prepared from the fluorine-containing epoxy resin prepared in Examples 1-5 were subjected to impact resistance, water resistance, wear resistance and weather resistance tests, and the test results are shown in Table 1 below.

[0087] Among them, the test method of the impact resistance of the epoxy resin coating refers to the standard GB / T 1732-1993; the water resistance of the epoxy resin coating is tested by using a LSA100 type surface contact angle tester of LAUDA Scientific Company in Germany; the wear resistance of the epoxy resin coating is tested according to the standard GB / T 1768-2006; and the weather resistance of the epoxy resin coating is tested according to the standard ASTM G154-2016.

[0088] Table 1 Performance test results of the cured fluorine-containing epoxy resin coating prepared from the fluorine-containing epoxy resin of Examples 1-5

[0089]

[0090] As can be seen from the above table, the surface of the fluorine-containing epoxy resin coating prepared from the fluorine-containing epoxy resin of Examples 1-5 is enriched with a large number of fluorine atoms, so the contact angle of the coating is greater than 90°, showing good hydrophobicity; further, the C-F bond length is short and the bond energy is large, due to the introduction of the C-F bond, the fluorine atoms are distributed in a spiral shape along the carbon chain, enhancing the shielding effect of the fluorine atoms on the C-C bond, the electronegativity of the fluorine atoms is large, the repulsive force between the fluorine atoms is large, and further the intermolecular force of the fluorine-containing epoxy resin is small, so that the surface energy of the fluorine-containing epoxy resin is low, the friction coefficient is low, and the wear rate is low, showing good wear resistance; the surface of the fluorine-containing epoxy resin coating prepared from the fluorine-containing epoxy resin of Examples 1-5 is smooth and beautiful, and due to the introduction of the C-F bond in the fluorine-containing epoxy resin of the present application, the bond energy of the C-F bond is high and the proportion of the C-F bond in the molecular chain segment is high, so that the coating shows excellent impact resistance and weather resistance.

[0091] For the sake of explanation, the foregoing descriptions have been presented in terms of specific embodiments. However, it is to be appreciated that specific embodiments described herein are not intended to limit the scope of the present application, which is defined with reference to the following claims. Various modifications and changes can be made thereto by those skilled in the art which fall within the scope of the present application as defined by the following claims. The embodiments were chosen and described in order to explain the principles of the application and the practical application and to enable others skilled in the art to understand for implementing various embodiments and with various modifications as are suited to the particular use contemplated.

Claims

1. A fluorinated epoxy resin, characterized in that, The fluorinated epoxy resin is made from the following raw materials: 2-(but-3-enoxy)-3-hydroxypropyl acetate, maleic anhydride, perfluoro-1-octanol and oxidizing agent; The molar ratio of 2-(but-3-enoxy)-3-hydroxypropyl acetate to maleic anhydride is (1.1-1.3):1; the molar ratio of the first intermediate to perfluoro-1-octanol is 1:(1.1-1.3); and the molar ratio of the second intermediate to the oxidant is 1:(2.1-2.3). The first intermediate was prepared by reacting 2-(but-3-enoxy)-3-hydroxypropyl acetate with maleic anhydride, and the second intermediate was prepared by reacting the first intermediate with the perfluoro-1-octanol. The fluorinated epoxy resin has the following general formula:

2. A method for preparing a fluorinated epoxy resin, characterized in that, The method includes: 2-(but-3-enoxy)-3-hydroxypropyl acetate and maleic anhydride were subjected to an esterification reaction at 90–120 °C for 3–6 h to obtain the first intermediate product. The first intermediate product, perfluoro-1-octanol, and concentrated sulfuric acid were mixed and subjected to an esterification reaction at a temperature of 90–120°C for 3–6 hours to obtain the second intermediate product. The oxidant is dissolved in a solvent and then slowly added dropwise to the second intermediate product. An epoxidation reaction is carried out at a reaction temperature of 5℃ to 15℃ for 8h to 12h to obtain a fluorinated epoxy resin. The molar ratio of the second intermediate product to the oxidant is 1:(2.1-2.3), the oxidant is m-chloroperoxybenzoic acid, and the solvent is dichloromethane; The reaction of the method includes 3. The method for preparing the fluorinated epoxy resin as described in claim 2, characterized in that, The molar ratio of 2-(but-3-enoxy)-3-hydroxypropyl acetate to maleic anhydride is (1.1 to 1.3):

1.

4. The method for preparing the fluorinated epoxy resin as described in claim 2, characterized in that, The molar ratio of the first intermediate product to perfluoro-1-octanol is 1:(1.1 to 1.3), and the mass of the concentrated sulfuric acid is 2% to 3% of the mass of the perfluoro-1-octanol.

5. An application of a fluorinated epoxy resin, characterized in that, This includes the application of the fluorinated epoxy resin as described in claim 1 in the fields of coatings, electronic packaging, adhesives, and advanced materials.

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