Synthesis method and application of flexible double bond hybrid epoxy resin

Abstract

The application provides a synthesis method and application of a flexible double bond hybrid epoxy resin, and relates to the technical field of epoxy resin materials. The synthesis method of the flexible double bond hybrid epoxy resin comprises subjecting 2,2-alkene tetradecyl heptyl bisphenol A and epichlorohydrin to a nucleophilic substitution reaction to obtain the flexible double bond hybrid epoxy resin containing a flexible long carbon chain structure and a double bond structure. According to the technical scheme, long carbon chains and double bond structures are introduced into the epoxy resin to obtain the flexible double bond hybrid epoxy resin. Due to the existence of the flexible carbon chain, the disadvantage of insufficient toughness of the epoxy resin after curing can be effectively improved. Moreover, the flexible double bond hybrid epoxy resin also contains a double bond structure. When the double bond in the nitrile rubber preferentially reacts during the toughening modification of the flexible double bond hybrid epoxy resin, the compatibility between the epoxy resin and the toughening agent is improved, and the carbon-carbon double bond in the nitrile rubber can be eliminated, and the heat resistance and the cohesive strength of the epoxy resin film are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular polymer materials, in particular to a synthesis method and application of a flexible double bond hybrid epoxy resin. BACKGROUND

[0002] Epoxy resin (EP) is a thermosetting resin with an organic compound as a skeleton, and a three-dimensional network structure polymer is formed after a thermosetting polymer and a curing agent are crosslinked. Epoxy resin has excellent physical and mechanical properties, electrical insulation properties, heat resistance and bonding properties, and is widely used in the semiconductor industry. With the development of high integration and thinning of semiconductor technology, the requirements for epoxy resin adhesives as semiconductor packaging materials are also increasing. The semiconductor packaging material is composed of epoxy resin, curing agent and other additives, and the epoxy resin is one of the important raw materials that determine the packaging material. However, as a general epoxy resin material, due to the high crosslinking density and internal stress of the resin, there are a large number of hydroxyl groups in the crosslinked network structure, which makes the stability poor, and it cannot meet the special use requirements of epoxy resin crosslinking agent for the development of semiconductors in recent years. In addition, due to the high crosslinking density of the pure epoxy resin cured product, the crosslinking network skeleton is rigid, which makes it difficult for the molecular chains to slide relative to each other, and thus the product has poor toughness, heat resistance and impact resistance, which limits its application.

[0003] At present, the existing technology usually adds a toughening agent to improve the toughness of the epoxy resin, but the compatibility of the toughening agent with the epoxy resin is generally poor. For example, nitrile rubber, as a commonly used epoxy resin toughening agent, especially the double bonds contained in the nitrile rubber, cause the epoxy resin to have higher activity, resulting in poor thermal stability of the adhesive film.

[0004] To solve the above technical problems, the present application provides a flexible double bond hybrid epoxy resin with a long carbon chain and a double bond structure, which has both flexibility and activity. When crosslinked with nitrile rubber, the double bond structure of the hybrid epoxy resin preferentially crosslinks with the double bond structure of the nitrile rubber, thereby eliminating the double bond structure of the nitrile rubber, and the resulting modified epoxy resin has a more stable structure, and after modification by nitrile rubber, it has stronger toughness. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a synthesis method and application of a flexible double bond hybrid epoxy resin, which introduces a double bond and a flexible long chain structure into the structure of the epoxy resin, and obtains a modified epoxy resin with both thermal stability and toughness by crosslinking with nitrile rubber.

[0006] In order to achieve the above purpose, the present application provides the following technical scheme:

[0007] A method for synthesizing a flexible double-bond hybrid epoxy resin involves subjecting 2,2-entetradecylheptylbisphenol A and epichlorohydrin to a nucleophilic substitution reaction to obtain a flexible double-bond hybrid epoxy resin containing both a flexible long carbon chain structure and a double bond structure.

[0008] As a preferred embodiment, the method for synthesizing the flexible double-bond hybrid epoxy resin includes the following steps: 2,2-entetradecylheptylbisphenol A and epichlorohydrin are mixed evenly under normal pressure, then heated to 80-90°C and stirred for 1-2 hours; then cooled to 50-70°C and solid sodium hydroxide is added evenly over 5-8 hours, and the mixture is reacted at 50-60°C for 7-10 hours to obtain the double-bond hybrid flexible epoxy resin.

[0009] Preferably, the mass ratio of 2,2-entetradecylheptylbisphenol A to epichlorohydrin is 1:(3-4).

[0010] Preferably, the mass ratio of solid sodium hydroxide to 2,2-entetradecylheptylbisphenol A is 0.5:(1-1.5).

[0011] As a preferred embodiment, the preparation method of 2,2-entetradecylheptylbisphenol A includes: reacting bisphenol A and entetradecylheptyl ether under acidic conditions under N2 protection to prepare 2,2-entetradecylheptylbisphenol A.

[0012] As a preferred embodiment, the preparation method of 2,2-entetradecylheptylbisphenol A includes: stirring and mixing entetradecylheptyl ether, bisphenol A and water at room temperature and pressure until homogeneous; then, adding hydrochloric acid solution within 20 minutes to react; and finally, distilling at atmospheric pressure to obtain 2,2-entetradecylheptylbisphenol A.

[0013] Preferably, the molar ratio of ethtetradecylheptyl ether to bisphenol A is 1:1.

[0014] Preferably, the reaction is carried out at 40–60°C for 1–3 hours.

[0015] Preferably, the hydrochloric acid solution has a mass fraction of 20%.

[0016] As one of the objectives of the invention, the present invention also provides a flexible double-bond hybrid epoxy resin, which is prepared by the above-described synthesis method of the flexible double-bond hybrid epoxy resin.

[0017] As one of the objectives of the invention, the present invention also provides a modified epoxy resin prepared by crosslinking the above-mentioned flexible double-bond hybrid epoxy resin with nitrile rubber.

[0018] As one of the objectives of this invention, a method for preparing a modified epoxy resin is also provided, comprising the following steps:

[0019] dissolving the flexible double bond hybrid epoxy resin in ethyl acetate to form a flexible double bond hybrid epoxy resin solution;

[0020] dissolving the nitrile rubber in butanone to form a nitrile rubber solution;

[0021] After the flexible double bond hybrid epoxy resin solution and the nitrile rubber solution are uniformly mixed, an initiator is added, and a crosslinking reaction is carried out by heating to obtain the modified epoxy resin.

[0022] Preferably, the crosslinking reaction is carried out at 60-80°C for 3-8h.

[0023] Preferably, the initiator is a peroxide initiator; preferably, the initiator is any one of BPO, DTBP, MEKP, and CHP.

[0024] As one of the purposes of the application, the application also provides an epoxy film, wherein the base material is the modified epoxy resin described above.

[0025] The application has the following beneficial technical effects: by using the technical scheme of the application, long carbon chains and double bond structures are introduced into the epoxy resin to obtain a flexible double bond hybrid epoxy resin. On the one hand, the presence of the flexible carbon chains can effectively improve the disadvantage of insufficient toughness of the epoxy resin after curing. On the other hand, the flexible double bond hybrid epoxy resin also contains double bond structures. When the flexible double bond hybrid epoxy resin is toughened and modified, the double bonds in the nitrile rubber preferentially react, which improves the compatibility between the epoxy resin and the toughening agent, and also eliminates the carbon-carbon double bonds in the nitrile rubber, thereby improving the heat resistance and cohesive strength of the epoxy resin film. DETAILED DESCRIPTION

[0026] To make the purposes, technical solutions, and advantages of the embodiments of the application clearer, the technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments of the application.

[0027] The application provides a flexible double bond hybrid epoxy resin. Long carbon chains are introduced into the epoxy resin. The presence of the flexible carbon chains can effectively improve the disadvantage of insufficient toughness of the epoxy resin after curing. Meanwhile, the flexible double bond hybrid epoxy resin also contains double bond structures. When the flexible double bond hybrid epoxy resin is toughened and modified, the double bonds in the nitrile rubber preferentially react, which improves the compatibility between the epoxy resin and the toughening agent, and also eliminates the carbon-carbon double bonds in the nitrile rubber, thereby improving the heat resistance and cohesive strength of the epoxy resin film.

[0028] Specifically, the application provides a preparation method of the flexible double bond hybrid epoxy resin, which comprises the following steps: synthesizing 2,2-alkenyl tetradecyl heptyl bisphenol A from bisphenol A and alkenyl tetradecyl heptyl ether, and then synthesizing the flexible double bond hybrid epoxy resin from the 2,2-alkenyl tetradecyl heptyl bisphenol A and epichlorohydrin. The technical principle of the synthesis is as follows:

[0029] 1) Synthesis of 2,2-alkenyl tetradecyl heptyl bisphenol A:

[0030]

[0031] The ether bond is dissociated under the catalysis of an acid to generate a tert-butyl cation which is more stable than a methyl cation, and the tert-butyl cation attacks the ortho position of the phenolic hydroxyl group to perform a nucleophilic substitution reaction at the ortho position. Since the phenolic hydroxyl group has poor nucleophilicity, the phenolic hydroxyl group does not participate in the reaction in the reaction process, and thus the obtained synthesis product is the 2,2-alkenyl tetradecyl heptyl bisphenol A.

[0032] 2) Synthesis of the double bond hybrid flexible epoxy resin:

[0033]

[0034] 3) Crosslinking of the epoxy / nitrile rubber:

[0035]

[0036] The double bond hybrid flexible epoxy resin obtained has a long carbon chain, which can improve the disadvantage of poor toughness of the epoxy resin after curing. Further, the flexible double bond hybrid epoxy resin is reacted with the nitrile rubber to generate a flexible epoxy / nitrile rubber crosslinking product (modified epoxy resin). The double bond in the epoxy resin and the double bond in the nitrile rubber preferentially perform a crosslinking reaction, which greatly improves the compatibility between the epoxy resin and the nitrile rubber, improves the toughening effect of the rubber, and reacts the double bond in the rubber, which greatly improves the heat resistance and the cohesive strength.

[0037] The technical scheme of the application is described in detail below through specific examples.

[0038] Example 1

[0039] The example provides a modified epoxy resin which is prepared by crosslinking reaction of the nitrile rubber as a toughening agent and the flexible double bond hybrid epoxy resin. Specifically, the specific steps of the preparation comprise the following steps:

[0040] (1) Synthesis of alkenyl tetradecyl heptyl ether

[0041] The preparation method of the alkenyl tetradecyl heptyl ether comprises the following steps:

[0042] Under N2 protection, 880 g of n-heptanol, 1050 g of tetradecenol, and 10 g of cuprous chloride were added into a three-neck flask, stirred at room temperature for 20 min at a rotation speed of 300 R / min, and then 15 mL of concentrated sulfuric acid was added dropwise at a rate of 1 mL / min, slowly heated to 90°C, and water was removed by refluxing during stirring. After stirring for 8 h, it was cooled to room temperature, neutralized to neutral with 10% sodium hydroxide aqueous solution, and then washed with water, dried, and fractionated to obtain enetetradecyl heptyl ether.

[0043] The infrared spectrum data of the reaction product are as follows: IR (KBr, cm -1 ): ~3400 cm -1 -OH characteristic peak disappeared, and two -C-O-C- bending vibration absorption peaks appeared at 950 cm -1 and 890 cm -1 , confirming that the prepared substance is enetetradecyl heptyl ether.

[0044] (2) Synthesis of 2,2- enetetradecyl heptyl bisphenol A

[0045] Under N2 protection, 71.5 g of enetetradecyl heptyl ether, 57 g of bisphenol A, and 100 g of water were sequentially added into a three-neck flask, stirred at room temperature for 30 min at a rotation speed of 300 R / min, and then 20% hydrochloric acid aqueous solution was added within 20 min, and reacted at 50°C for 2 h. Then 2,2- enetetradecyl heptyl bisphenol A was obtained by normal pressure distillation.

[0046] (3) Synthesis of double bond hybrid flexible epoxy resin:

[0047] 2,2- enetetradecyl heptyl bisphenol A 200 g, and epoxy chloropropane 600 g were put into a three-neck flask, stirred at a rotation speed of 300 R / min under normal pressure, heated to 80°C, and reacted for 1 h. Then 100 g of solid NaOH was uniformly added within 6 h after the temperature was reduced to 50°C. After reacting at 50°C for 9 h, the excess epoxy chloropropane was recovered under reduced pressure to obtain a double bond hybrid flexible epoxy resin.

[0048] (4) Crosslinking of epoxy / nitrile rubber:

[0049] 50 g of flexible double bond hybrid epoxy resin and 50 g of ethyl acetate solution were added into a three-neck flask, and then 20 g of 20% nitrile rubber solution dissolved in butanone was added. The mixture was stirred at a rotation speed of 300 R / min under normal pressure, heated to 70°C, and 40 g of 50% BPO solution dissolved in ethyl acetate was added dropwise slowly within 3 h. After stirring at 70°C for 5 h, the obtained flexible epoxy / nitrile rubber crosslinking product was a modified epoxy resin by ethanol filtration.

[0050] The modified epoxy resin prepared in the above reaction was dissolved with ethyl ester to obtain a solution with a solid content of 40wt%, 200 parts, 10 parts of dicyandiamide as a curing agent, 20 parts of fumed silica (QS-102) as a filler, 2 parts of coupling agent KH-550, and 1 part of leveling agent BYK-333 were added, and then stirred uniformly, coated on a release film, baked in a 100℃ oven for 2 min, and a special flexible double bond hybrid epoxy resin film with a thickness of 50μm was obtained.

[0051] Example 2

[0052] The difference between this example and Example 1 is that 10g of a 20% nitrile rubber solution dissolved in butanone in advance was added during the crosslinking of the epoxy / nitrile rubber, and the other steps were the same as in Example 1.

[0053] Example 3

[0054] The difference between this example and Example 1 is that 30g of a 20% nitrile rubber solution dissolved in butanone in advance was added during the crosslinking of the epoxy / nitrile rubber, and the other steps were the same as in Example 1.

[0055] Comparative Example 1

[0056] The difference between this comparative example and Example 1 is that the nitrile rubber was directly added to the ordinary bisphenol A epoxy resin (E-44), and the other steps were the same as in Example 1.

[0057] The film prepared in the examples and comparative examples of the present application was tested for performance.

[0058] The test method included: the film surface of the film was attached to the surface of a SUS test plate and pre-pressed for 10 seconds at 60℃ and 0.1MPa pressure, and then the release film was torn off, another SUS test plate was attached, and then pressed at a pressure of 0.3MPa and a temperature of 160℃ for 60 seconds, then placed in a 140℃ oven for 30 minutes, then taken out and left to stand at room temperature for 24 hours, and then tested for initial, room temperature and 100℃ shear force after double 85 test for 1000 hours using a high and low temperature electronic tensile testing machine (Instron 3400 type). The test results are shown in Table 1.

[0059] Table 1 Performance of the film prepared in the examples and comparative examples of the present application

[0060]

[0061] As can be seen from Table 1, the flexible double bond hybrid epoxy resin provided by the present application has no significant change in dynamic shear force at room temperature and 100℃ for 1000h compared with ordinary bisphenol A epoxy resin, indicating that the epoxy resin film has excellent toughness, heat resistance and cohesive strength.

[0062] Obviously, by using the technical scheme of the present application, on the one hand, the introduction of the flexible carbon chain into the epoxy resin can effectively improve the disadvantage of insufficient toughness of the cured epoxy resin; on the other hand, the flexible double bond hybrid epoxy resin also contains a double bond structure, when it is toughened and modified, the compatibility between the epoxy resin and the toughening agent is improved by preferentially reacting with the double bond in the nitrile rubber, and the carbon-carbon double bond in the nitrile rubber can be eliminated, thereby improving the heat stability and cohesive strength of the epoxy resin film.

[0063] The above are only preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. For those skilled in the art, the present application can have various changes and modifications. Any changes, modifications, replacements, integrations and parameter changes made to these embodiments within the spirit and principles of the present application by conventional substitutions or to achieve the same functions without departing from the principles and spirit of the present application fall within the protection scope of the present application.

Claims

1. A method for synthesizing a flexible double-bond hybrid epoxy resin, characterized in that, Nucleophilic substitution reaction of 2,2-entetradecylheptylbisphenol A and epichlorohydrin yields a flexible double-bond hybrid epoxy resin containing both a flexible long carbon chain structure and a double bond structure. The specific steps include: mixing 2,2-entetradecylheptylbisphenol A and epichlorohydrin evenly under normal pressure, first heating to 80~90℃ and stirring for 1~2h; then cooling to 50~70℃ and uniformly adding solid sodium hydroxide within 5~8h, and reacting at 50~60℃ for 7~10h to obtain the double bond hybrid flexible epoxy resin; The mass ratio of 2,2-entetradecylheptylbisphenol A to epichlorohydrin is 1:(3~4); The mass ratio of solid sodium hydroxide to 2,2-entetradecylheptylbisphenol A is 0.5:(1~1.5).

2. The method for synthesizing the flexible double-bond hybrid epoxy resin according to claim 1, characterized in that, The preparation method of 2,2-entetradecylheptylbisphenol A includes: under N2 protection, bisphenol A and entetradecylheptyl ether are reacted under acidic conditions to prepare 2,2-entetradecylheptylbisphenol A.

3. The method for synthesizing the flexible double-bond hybrid epoxy resin according to claim 2, characterized in that, The preparation method of 2,2-entetradecylheptylbisphenol A specifically includes: stirring and mixing entetradecylheptyl ether, bisphenol A and water at room temperature and pressure until homogeneous; then, adding hydrochloric acid solution within 20 minutes to react; and finally, distilling at atmospheric pressure to obtain 2,2-entetradecylheptylbisphenol A.

4. The method for synthesizing the flexible double-bond hybrid epoxy resin according to claim 3, characterized in that, The molar ratio of ethtetradecylheptyl ether to bisphenol A is 1:

1.

5. The method for synthesizing the flexible double-bond hybrid epoxy resin according to claim 3, characterized in that, The reaction conditions are 40~60℃ for 1~3h.

6. The method for synthesizing the flexible double-bond hybrid epoxy resin according to claim 3, characterized in that, The hydrochloric acid solution has a mass fraction of 20%.

7. A flexible double-bond hybrid epoxy resin, prepared by the synthesis method described in any one of claims 1-6.

8. A modified epoxy resin, prepared by the synthesis method according to any one of claims 1-6, comprising a flexible double-bond hybrid epoxy resin, or prepared by crosslinking the flexible double-bond hybrid epoxy resin according to claim 7 with nitrile rubber.

9. A method for preparing the modified epoxy resin as described in claim 8, characterized in that, Includes the following steps: A flexible double-bond hybrid epoxy resin was dissolved in ethyl acetate to form a flexible double-bond hybrid epoxy resin solution; Nitrile rubber is dissolved in butanone to form a nitrile rubber solution; After the flexible double-bond hybrid epoxy resin solution and the nitrile rubber solution are mixed evenly, an initiator is added, and the mixture is heated to carry out a crosslinking reaction to obtain the modified epoxy resin.

10. The method for preparing the modified epoxy resin according to claim 9, characterized in that, The crosslinking reaction is carried out at 60-80°C for 3-8 hours.

11. The method for preparing the modified epoxy resin according to claim 9, characterized in that, The initiator is a peroxide initiator.

12. The method for preparing the modified epoxy resin according to claim 9, characterized in that, The initiator is any one of BPO, DTBP, MEKP, and CHP.

13. An epoxy film, comprising at least a matrix material; said matrix material being the modified epoxy resin as described in claim 8.

Images