A high-toughness, heat-resistant organosilicon epoxy resin and its preparation method and application

Abstract

The present application relates to the technical field of modified epoxy resins, in particular to a high-toughness and heat-resistant organosilicon epoxy resin and its preparation method and application, which can solve the problem that epoxy resin products have poor toughness and temperature resistance due to the molecular structure characteristics of epoxy resin. The high-toughness and heat-resistant organosilicon epoxy resin is made of the following raw materials: 1,4-butanediol, maleic anhydride, hydroxy silicone oil and oxidant; wherein the molar ratio of maleic anhydride to 1,4-butanediol is (2-2.5): 1, and the molar ratio of hydroxy silicone oil to the first intermediate product is (2-3): 1; the molar ratio of the second intermediate product to the oxidant is 1: (2-2.1); the first intermediate product is prepared by the reaction of maleic anhydride and 1,4-butanediol, and the second intermediate product is prepared by the reaction of the first intermediate product and the oxidant.

Description

Technical Field

[0001] The present application relates to the technical field of modified epoxy resins, and in particular to a high-toughness, temperature-resistant organosilicon epoxy resin and a preparation method and application thereof. Background Art

[0002] Epoxy resin is a general term for polymers containing two or more epoxy groups in its molecule. It is a condensation product of epichlorohydrin and bisphenol A or polyols. Due to the chemical reactivity of the epoxy group, it can be ring-opened with various compounds containing active hydrogen, which then cures and cross-links to form a network structure, making it a thermosetting resin. Epoxy resin is widely used as an encapsulation material in semiconductor devices, integrated circuits, consumer electronics, automotive, aerospace, and military applications.

[0003] However, epoxy resins are prone to aging, bond breaking, and decomposition at high temperatures, resulting in poor temperature resistance. Furthermore, epoxy resins have a high cross-linking density and are brittle and have poor toughness. Summary of the Invention

[0004] In order to solve the problem that epoxy resin products have poor temperature resistance and poor toughness due to the molecular structure characteristics of epoxy resin, the present application provides a high-toughness and temperature-resistant silicone epoxy resin and its preparation method and application.

[0005] The embodiment of the present application is implemented as follows:

[0006] The present invention provides a high-toughness and heat-resistant organosilicon epoxy resin, which is made from the following raw materials: 1,4-butanediol, maleic anhydride, hydroxy silicone oil and an oxidant;

[0007] The molar ratio of maleic anhydride to 1,4-butanediol is (2-2.5):1, the molar ratio of hydroxy silicone oil to the first intermediate product is (2-3):1; and the molar ratio of the second intermediate product to the oxidant is 1:(2-2.1).

[0008] The first intermediate product is prepared by reacting the maleic anhydride with 1,4-butanediol, and the second intermediate product is prepared by reacting the first intermediate product with the oxidant.

[0009] The present application also provides a method for preparing a high-toughness and heat-resistant organosilicon epoxy resin, the method comprising:

[0010] Taking maleic anhydride and 1,4-butanediol, and performing an esterification reaction under first preset conditions to obtain a first intermediate product;

[0011] adding hydroxy silicone oil to the first intermediate product, and performing an esterification reaction under second preset conditions to obtain a second intermediate product;

[0012] The second intermediate product and an oxidant are taken and subjected to an epoxidation reaction under third preset conditions to obtain an organosilicon epoxy resin.

[0013] In some embodiments, maleic anhydride and 1,4-butanediol are subjected to an esterification reaction under first preset conditions to obtain a first intermediate product, comprising:

[0014] Dissolving maleic anhydride, 1,4-butanediol, and the first catalyst in a solvent, performing an esterification reaction at a reaction temperature of 60° C. to 80° C., performing condensation reflux during the esterification reaction, and reacting for 1 hour to 2.5 hours to obtain the first intermediate product;

[0015] Wherein, the molar ratio of maleic anhydride to 1,4-butanediol is (2-2.5):1.

[0016] In some embodiments, adding hydroxy silicone oil to the first intermediate product and performing an esterification reaction under the second preset conditions to obtain a second intermediate product comprises:

[0017] Add hydroxy silicone oil and a second catalyst to the first intermediate product, and react at a reaction temperature of 60° C. to 80° C. for 4 to 8 hours to obtain the second intermediate product;

[0018] Wherein, the molar ratio of the hydroxy silicone oil to the first intermediate product is (2-3):1.

[0019] In some embodiments, the second intermediate product and an oxidant are subjected to an epoxidation reaction under third preset conditions to obtain an organosilicon epoxy resin, comprising:

[0020] Slowly add the oxidant dropwise to the second intermediate product cooled to room temperature, raise the temperature to 25°C to 40°C, and react at a reaction temperature of 25°C to 40°C for 2h to 5h to obtain a crude product;

[0021] performing reduced pressure distillation on the crude product to obtain the organosilicon epoxy resin;

[0022] The molar ratio of the second intermediate product to the oxidant is 1:(2-2.1), and the oxidant is m-chloroperoxybenzoic acid.

[0023] In some embodiments, the first catalyst is anhydrous sodium acetate or aluminum chloride, and the mass of the first catalyst is 0.05% to 0.1% of the sum of the mass of maleic anhydride and 1,4-butanediol.

[0024] In some embodiments, the second catalyst is concentrated sulfuric acid, phosphoric acid or benzenesulfonic acid, and the mass of the second catalyst is 0.05% to 0.1% of the sum of the mass of the first intermediate product and the hydroxy silicone oil used for the esterification reaction under the second preset conditions.

[0025] In some embodiments, the solvent is acetone or dimethylformamide.

[0026] The embodiments of the present application also provide an application of a high-toughness, heat-resistant silicone epoxy resin, including applications of the high-toughness, heat-resistant silicone epoxy resin in the fields of coatings, electronic packaging, and adhesives.

[0027] The beneficial effects of the present application are as follows: the present application first uses maleic anhydride and 1,4-butanediol as raw materials to carry out an esterification reaction to obtain a first intermediate product containing a carboxyl group; then, the carboxyl group in the first intermediate product undergoes a condensation reaction with Si-OH in hydroxy silicone oil to obtain a second intermediate product containing an organic silicon segment and a carbon-carbon double bond; finally, the carbon-carbon double bond in the second intermediate product molecule is oxidized by an oxidant to generate an epoxy group, thereby finally obtaining a high-toughness and heat-resistant organic silicon epoxy resin;

[0028] The present invention introduces organic silicon segments into the molecular structure. The organic silicon segments have advantages such as low surface tension, high thermal stability, good electrical insulation, and good water resistance. Therefore, the prepared organic silicon epoxy resin has good heat resistance and water resistance. Furthermore, the toughness of the cured organic silicon epoxy resin is enhanced because the organic silicon segments have a cross-linked network structure.

[0029] The organosilicon epoxy resin prepared in the present application combines the advantages of organosilicon resin and epoxy resin, and has excellent adhesion and electrical insulation as well as excellent water resistance, heat resistance and toughness. At the same time, the synthesis process of organosilicon epoxy resin is simple and can be industrialized. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, a brief introduction will be given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0031] Figure 1 This is the H NMR spectrum provided in the examples of this application. DETAILED DESCRIPTION

[0032] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0033] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0034] Herein, all features such as values, amounts, amounts, and concentrations defined in numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to include and specifically disclose all possible subranges and individual values ​​within the range (including integers and fractions).

[0035] Herein, unless otherwise specified, “comprising”, “including”, “containing”, “having” or similar terms cover the meanings of “consisting of” and “consisting mainly of”, for example, “A contains a” covers the meanings of “A contains a and other” and “A only contains a”.

[0036] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0037] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0038] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0039] The present invention provides a high-toughness and heat-resistant organosilicon epoxy resin, which is made from the following raw materials: 1,4-butanediol, maleic anhydride, hydroxy silicone oil, and an oxidant;

[0040] The molar ratio of maleic anhydride to 1,4-butanediol is (2-2.5):1, the molar ratio of hydroxy silicone oil to the first intermediate product is (2-3):1; the molar ratio of the second intermediate product to the oxidant is 1:(2-2.1);

[0041] The first intermediate product is prepared by reacting the maleic anhydride with 1,4-butanediol, and the second intermediate product is prepared by reacting the first intermediate product with the oxidant;

[0042] In some embodiments, the oxidizing agent is meta-chloroperoxybenzoic acid (ie, mCPBA).

[0043] The present application also provides a method for preparing a high-toughness and heat-resistant organosilicon epoxy resin, the method comprising:

[0044] Taking maleic anhydride and 1,4-butanediol, and performing an esterification reaction under first preset conditions to obtain a first intermediate product;

[0045] adding hydroxy silicone oil to the first intermediate product, and performing an esterification reaction under second preset conditions to obtain a second intermediate product;

[0046] The second intermediate product and an oxidant are taken and subjected to an epoxidation reaction under third preset conditions to obtain an organosilicon epoxy resin.

[0047] In some embodiments, the principle equation for preparing the high-toughness and heat-resistant organosilicon epoxy resin of the present application is also provided:

[0048]

[0049] Among them, n=50~100.

[0050] The present application is further described below with reference to specific embodiments.

[0051] Example 1

[0052] In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, 100 mL of acetone was added, followed by 9 g of 1,4-butanediol, 19.6 g of maleic anhydride, and 0.0143 g of anhydrous sodium acetate. The temperature was raised to 60° C., condensed and refluxed, and the reaction was carried out for 1 hour to obtain a first intermediate product.

[0053] Reserve 10 g of the first intermediate product in a four-necked flask, add 20 g of hydroxy silicone oil and 0.0335 g of concentrated sulfuric acid, heat to 60 ° C, and react for 4 hours. After the reaction is completed, cool the reaction solution in the four-necked flask to room temperature to obtain a second intermediate product;

[0054] After slowly adding m-chloroperoxybenzoic acid into a four-necked flask at 5°C, the temperature was raised to 25°C, and the reaction was carried out for 2 hours to obtain a crude product;

[0055] The crude product is subjected to reduced pressure distillation to remove acetone, thereby obtaining a high-toughness and temperature-resistant organosilicon epoxy resin.

[0056] Example 2

[0057] In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, 100 mL of DMF (i.e., dimethylformamide) was added, followed by 9 g of 1,4-butanediol, 24.5 g of maleic anhydride, and 0.0335 g of aluminum trichloride. The temperature was raised to 80° C., condensed and refluxed, and the reaction was carried out for 2.5 hours to obtain the first intermediate product;

[0058] Reserve 15g of the first intermediate product in a four-necked flask, add 45g of hydroxy silicone oil and 0.06g of phosphoric acid, heat to 80°C, and react for 8h. After the reaction is completed, cool the reaction solution in the four-necked flask to room temperature to obtain a second intermediate product;

[0059] After slowly adding m-chloroperoxybenzoic acid into a four-necked flask at 10°C, the system was heated to 40°C and reacted for 5 hours to obtain a crude product;

[0060] The crude product is subjected to reduced pressure distillation to remove DMF, thereby obtaining a high-toughness and temperature-resistant organosilicon epoxy resin.

[0061] Example 3

[0062] 100 mL of DMF was added to a four-necked flask equipped with a stirring device, a thermometer, and a condenser, followed by 9 g of 1,4-butanediol, 19.8 g of maleic anhydride, and 0.023 g of anhydrous sodium acetate. The temperature was raised to 70° C., condensed and refluxed, and the reaction was completed after 2 h to obtain the first intermediate product.

[0063] 18 g of the first intermediate product was reserved in a four-necked flask, and 41.4 g of hydroxy silicone oil and 0.0356 g of benzenesulfonic acid were added thereto. The temperature was raised to 70° C. and the reaction was carried out for 6 h. After the reaction was completed, the reaction solution in the four-necked flask was cooled to room temperature to obtain a second intermediate product.

[0064] After slowly adding m-chloroperoxybenzoic acid into a four-necked flask at 12°C, the system was heated to 30°C and reacted for 3 hours to obtain a crude product;

[0065] The crude product is subjected to reduced pressure distillation to remove DMF, thereby obtaining a high-toughness and temperature-resistant organosilicon epoxy resin.

[0066] Example 4

[0067] In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, 100 mL of acetone was added, followed by 9 g of 1,4-butanediol, 19.6 g of maleic anhydride, and 0.0143 g of aluminum trichloride. The temperature was raised to 65°C, condensed and refluxed, and the reaction was continued for 2 h to obtain the first intermediate product.

[0068] 8 g of the first intermediate product was reserved in a four-necked flask, and 22.4 g of hydroxy silicone oil and 0.0213 g of concentrated sulfuric acid were added thereto. The temperature was raised to 75 ° C. and the reaction was carried out for 7 h. After the reaction was completed, the reaction solution in the four-necked flask was cooled to room temperature to obtain a second intermediate product;

[0069] After slowly adding m-chloroperoxybenzoic acid into a four-necked flask at 8°C, the system was heated to 35°C and reacted for 4 hours to obtain a crude product;

[0070] The crude product is subjected to reduced pressure distillation to remove acetone, thereby obtaining a high-toughness and temperature-resistant organosilicon epoxy resin.

[0071] Example 5

[0072] In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, 100 mL of DMF was added, followed by 9 g of 1,4-butanediol, 24.5 g of maleic anhydride, and 0.0335 g of anhydrous sodium acetate. The temperature was raised to 80°C, condensed and refluxed, and the reaction was continued for 2.5 h to obtain the first intermediate product.

[0073] Reserve 12 g of the first intermediate product in a four-necked flask, add 20 g of hydroxy silicone oil and 0.0335 g of concentrated sulfuric acid, heat to 65 ° C, and react for 5 hours. After the reaction is completed, cool the reaction solution in the four-necked flask to room temperature to obtain a second intermediate product;

[0074] After slowly adding m-chloroperoxybenzoic acid into a four-necked flask at 9°C, the system was heated to 25°C and reacted for 5 hours to obtain a crude product;

[0075] The crude product is subjected to reduced pressure distillation to remove DMF, thereby obtaining a high-toughness and temperature-resistant organosilicon epoxy resin.

[0076] Example 6

[0077] In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, 100 mL of DMF was added, followed by 9 g of 1,4-butanediol, 20.7 g of maleic anhydride, and 0.0267 g of anhydrous sodium acetate. The temperature was raised to 75°C, condensed and refluxed, and the reaction was continued for 2 h to obtain the first intermediate product.

[0078] Reserve 12 g of the first intermediate product in a four-necked flask, add 39 g of hydroxy silicone oil and 0.052 g of benzenesulfonic acid, heat to 65 ° C, and react for 8 hours. After the reaction is completed, cool the reaction solution in the four-necked flask to room temperature to obtain a second intermediate product;

[0079] After slowly adding m-chloroperoxybenzoic acid into a four-necked flask at 10°C, the system was heated to 32°C and reacted for 3 hours to obtain a crude product;

[0080] The crude product is subjected to reduced pressure distillation to obtain a high-toughness and temperature-resistant organosilicon epoxy resin.

[0081] In order to characterize the structural characteristics of a high-toughness and heat-resistant organosilicon epoxy resin, the high-toughness and heat-resistant organosilicon epoxy resin synthesized in Example 4 was subjected to nuclear magnetic resonance hydrogen spectrum test. The nuclear magnetic hydrogen spectrum is shown in FIG. Figure 1 The test results are shown below:

[0082] 1 H NMR (300MHz, DMSO): δ 6.35 (s, H), 4.06 (t, H), 4.00 (s, H), 1.61 (m, H), 0.14 (s, H) ppm.

[0083] It can be seen from the nuclear magnetic resonance data that the present invention successfully prepared a high-toughness and temperature-resistant silicone epoxy resin with a target structure.

[0084] The organosilicon epoxy resin prepared in Examples 1 to 6 was used to prepare an organosilicon epoxy resin cured coating, each having a coating thickness of 1 mm. Specifically, the organosilicon epoxy resin prepared in accordance with the methods described in Examples 1 to 6 was mixed with an epoxy curing agent, an initiator, and a reactive diluent in a certain proportion, stirred evenly, and applied to the surface of a glass plate. The coating was then cured in an oven at 60°C for 20 minutes to obtain a organosilicon epoxy resin cured coating.

[0085] The contact angle, dielectric constant, heat distortion temperature and tensile strength tests of each silicone epoxy resin are as follows:

[0086] The contact angle test was performed using a video contact angle meter. The epoxy resin in each embodiment was tested at least three times in parallel, and the average value was taken as the test result.

[0087] A TS2000-S universal testing machine was used to conduct mechanical property experiments, and the toughness of the epoxy resin in each example was determined by tensile strength.

[0088] The dielectric constant of the epoxy resin in each embodiment was tested using an Agilent 4294A precision impedance analyzer manufactured in the United States.

[0089] The heat distortion temperature of the epoxy resin prepared in each example was measured using a FYWK-300 heat distortion Vicat temperature meter. Before testing, the epoxy resin prepared in each example was poured into a polytetrafluoroethylene mold and cured under the curing conditions of 120°C / 2h + 140°C / 1h.

[0090] The test results are shown in Table 1.

[0091] Table 1 Test results of contact angle, dielectric constant, tensile strength and heat deformation temperature of high toughness and heat resistant silicone epoxy resin in each embodiment

[0092]

[0093] As shown in Table 1, the highly tough and heat-resistant silicone epoxy resin exhibits a contact angle of 102° to 127°, demonstrating excellent hydrophobicity. Furthermore, its tensile strength reaches 95 MPa, demonstrating significantly enhanced toughness. The dielectric constants of the silicone epoxy resins prepared in each example were also tested, and the dielectric constants ranged from 2.32 to 3.57, indicating that the silicone epoxy resins prepared by the present method also possess excellent electrical insulation properties, making them suitable for applications in coatings, electronic packaging, and adhesives.

[0094] For ease of explanation, the above description has been made in conjunction with specific embodiments. However, the above discussion of some embodiments is not intended to be exhaustive or to limit the embodiments to the specific forms disclosed above. Based on the above teachings, various modifications and variations can be obtained. The selection and description of the above embodiments are intended to better explain the principles and practical applications, so that those skilled in the art can better use the embodiments and various different variations of the embodiments suitable for specific use considerations.

Claims

1. A high-toughness, heat-resistant organosilicon epoxy resin, characterized in that: The organosilicon epoxy resin is prepared from the following raw materials: 1,4-butanediol, maleic anhydride, hydroxy silicone oil and an oxidant; The molar ratio of maleic anhydride to 1,4-butanediol is (2-2.5):1, the molar ratio of hydroxy silicone oil to the first intermediate product is (2-3):1; the molar ratio of the second intermediate product to the oxidant is 1:(2-2.1); The first intermediate product is prepared by reacting the maleic anhydride with 1,4-butanediol, and the second intermediate product is prepared by reacting the first intermediate product with the hydroxy silicone oil; The preparation method of the high-toughness and heat-resistant organosilicon epoxy resin comprises: Taking maleic anhydride and 1,4-butanediol, and performing an esterification reaction under first preset conditions to obtain a first intermediate product; adding hydroxy silicone oil to the first intermediate product, and performing an esterification reaction under second preset conditions to obtain a second intermediate product; The second intermediate product and an oxidant are taken and subjected to an epoxidation reaction under third preset conditions to obtain an organosilicon epoxy resin.

2. A method for preparing a high-toughness and heat-resistant organosilicon epoxy resin, characterized in that: The method comprises: Taking maleic anhydride and 1,4-butanediol, and performing an esterification reaction under first preset conditions to obtain a first intermediate product; adding hydroxy silicone oil to the first intermediate product, and performing an esterification reaction under second preset conditions to obtain a second intermediate product; The second intermediate product and an oxidant are taken and subjected to an epoxidation reaction under third preset conditions to obtain an organosilicon epoxy resin.

3. The method for preparing a high-toughness, heat-resistant organosilicon epoxy resin according to claim 2, wherein: Maleic anhydride and 1,4-butanediol are subjected to an esterification reaction under first preset conditions to obtain a first intermediate product, including: Dissolving maleic anhydride, 1,4-butanediol, and the first catalyst in a solvent, performing an esterification reaction at a reaction temperature of 60° C. to 80° C., performing condensation reflux during the esterification reaction, and reacting for 1 hour to 2.5 hours to obtain the first intermediate product; Wherein, the molar ratio of maleic anhydride to 1,4-butanediol is (2-2.5):

1.

4. The method for preparing a high-toughness, heat-resistant organosilicon epoxy resin according to claim 2, wherein: Adding hydroxy silicone oil to the first intermediate product and performing an esterification reaction under the second preset conditions to obtain a second intermediate product, comprising: Add hydroxy silicone oil and a second catalyst to the first intermediate product, react at a reaction temperature of 60° C. to 80° C. for 4 to 8 hours to obtain the second intermediate product; Wherein, the molar ratio of the hydroxy silicone oil to the first intermediate product is (2-3):

1.

5. The method for preparing a high-toughness, heat-resistant organosilicon epoxy resin according to claim 2, wherein: The second intermediate product and an oxidant are subjected to an epoxidation reaction under third preset conditions to obtain an organosilicon epoxy resin, comprising: Slowly add the oxidant dropwise to the second intermediate product cooled to room temperature, raise the temperature to 25°C to 40°C, and react at a reaction temperature of 25°C to 40°C for 2h to 5h to obtain a crude product; performing reduced pressure distillation on the crude product to obtain the organosilicon epoxy resin; The molar ratio of the second intermediate product to the oxidant is 1:(2-2.1), and the oxidant is m-chloroperoxybenzoic acid.

6. The method for preparing a high-toughness, heat-resistant organosilicon epoxy resin according to claim 3, wherein: The first catalyst is anhydrous sodium acetate or aluminum trichloride, and the mass of the first catalyst is 0.05% to 0.1% of the sum of the mass of maleic anhydride and 1,4-butanediol.

7. The method for preparing a high-toughness, heat-resistant organosilicon epoxy resin according to claim 4, wherein: The second catalyst is concentrated sulfuric acid, phosphoric acid or benzenesulfonic acid, and the mass of the second catalyst is 0.05% to 0.1% of the sum of the mass of the first intermediate product and the hydroxy silicone oil used for the esterification reaction under the second preset conditions.

8. The method for preparing a high-toughness, heat-resistant organosilicon epoxy resin according to claim 3, wherein: The solvent is acetone or dimethylformamide.

9. An application of a high-toughness and heat-resistant organosilicon epoxy resin, characterized in that: This includes the use of the high-toughness and temperature-resistant silicone epoxy resin as claimed in claim 1 in the fields of coating, electronic packaging and adhesives.

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