A silicone-modified spiro-orthoester epoxy resin, and a preparation method and application thereof

Abstract

The present application relates to the technical field of epoxy resin, and particularly relates to a kind of organic silicon modified spiro ortho ester epoxy resin and its preparation method and application.The present application discloses a kind of organic silicon modified spiro ortho ester epoxy resin, including the following raw materials by mole number: epoxy resin 1 mol, organic silicon crosslinking agent 2.0-2.1 mol, amino spiro ortho ester 1.1-1.2 mol.The present application discloses organic silicon modified spiro ortho ester epoxy resin, when applied to preparation into adhesive, with higher thermal decomposition temperature, the thermal expansion coefficient of interpenetration and with very high shear strength, tensile strength, can satisfy the reliability requirement of special electronic packaging.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy resin, in particular to a kind of organic silicon modified spiro ortho ester epoxy resin and its preparation method and application. BACKGROUND

[0002] Epoxy resin is widely used in electronic packaging material field with its excellent bonding performance, mechanical properties, electrical insulation and chemical stability, but some defects thereof cannot meet the requirements of electronic packaging alone.

[0003] Epoxy resin will produce volume shrinkage in the curing process, which makes the resin material inside produce shrinkage stress, is easy to produce stress concentration, causes the mechanical properties of material to be bad.And volume shrinkage will also affect the combination of resin and bonding interface, reduces the bonding effect.The common method to reduce the volume shrinkage rate of resin in the curing process is to add filler, which can only reduce the shrinkage to a certain extent but cannot offset it.Spiro ortho ester belongs to the expansion monomer, and there is no volume shrinkage in the polymerization process, even volume expansion can well offset the volume shrinkage of resin in the curing process, improve the toughness and interface bonding effect of polymer.

[0004] Epoxy resin also has the defects of large internal stress, poor toughness and thermal stability, while the organic silicon structure has the characteristics of good thermal stability, low surface energy, good toughness and high dielectric strength.Generally, the organic silicon modified epoxy resin reduces the Tg point of the resin due to the flexible chain segment of the organic silicon structure, and the thermal expansion coefficient is also large, and the density of epoxy group is reduced, and the crosslinking degree after curing is reduced, and the bulk strength is weakened. SUMMARY

[0005] In order to overcome the shortcomings of the prior art, the present application provides an organic silicon modified spiro ortho ester epoxy resin and its preparation method and application, which utilizes the reaction of isocyanate and alcohol hydroxyl to graft the organic silicon structure to the hydrogenated bisphenol A epoxy resin structure, to obtain a modified epoxy resin with organic siloxane structure, the organic silicon modified spiro ortho ester epoxy resin can combine the characteristics of organic silicon and epoxy resin, which can reduce the internal stress of epoxy resin, improve the mechanical properties, and increase the thermal stability;When applied to prepare adhesive, it has high thermal decomposition temperature, low thermal expansion coefficient, high shear strength and tensile strength, and can meet the reliability requirements of special electronic packaging.

[0006] The technical scheme adopted by the present application to solve its technical problems is:

[0007] The first purpose of the present application is to provide an organic silicon modified spiro ortho ester epoxy resin, which comprises the following raw materials in mole:

[0008] Epoxy resin 1mol

[0009] Silicone crosslinking agent 2.0-2.1 mol

[0010] Aminated spiro-ortho ester 1.1-1.2 mol.

[0011] Preferably, the epoxy resin is hydrogenated bisphenol A epoxy resin.

[0012] Preferably, the silicone crosslinking agent is isocyanate propyl trimethoxy silane.

[0013] Preferably, the aminated spiro-ortho ester is obtained by reacting spiro-ortho ester with ammonia gas under the action of a catalyst.

[0014] Preferably, the catalyst is alumina; the amount of the catalyst is 0.005-0.01 times the mole number of the spiro-ortho ester.

[0015] Preferably, the preparation method of the spiro-ortho ester comprises the following steps:

[0016] After the reaction of dipentaerythritol, di-n-butyl tin oxide and toluene, carbon disulfide is added for further reaction; after the reaction is completed, post-treatment is performed to obtain the spiro-ortho ester.

[0017] The second object of the present application provides a preparation method of silicone-modified spiro-ortho ester epoxy resin, which comprises the following steps:

[0018] 1) Amination modification of spiro-ortho ester

[0019] Aminated spiro-ortho ester is obtained by reacting spiro-ortho ester with ammonia gas under the action of a catalyst.

[0020] 2) Preparation of spiro-ortho ester modified epoxy resin

[0021] After mixing the epoxy resin and the aminated spiro-ortho ester, reaction is performed; after the reaction is completed, the spiro-ortho ester modified epoxy resin is obtained.

[0022] 3) Silicone modification

[0023] The spiro-ortho ester modified epoxy resin and the silicone crosslinking agent are reacted, and after the reaction is completed, the silicone-modified spiro-ortho ester epoxy resin is obtained.

[0024] Preferably, in step 2), the reaction condition is 100-110°C for 3-4h.

[0025] Preferably, in step 3), the reaction condition is 60-70°C for 12-16h.

[0026] A third object of the present application is to apply the organic silicon modified spiro-orthoester epoxy resin to adhesives.

[0027] The present application has the following advantages:

[0028] 1. The organic silicon modified spiro-orthoester epoxy resin of the present application has the following infrared spectrum data: the isocyanate absorption peak near 2200 cm-1 disappears, the absorption peak of the polyurethane structure appears at 1700 cm-1, 1530 cm-1, 3200 cm-1, and 3600 cm-1, which indicates that the isocyanate structure reacts with the alcohol hydroxyl group in the spiro-modified epoxy resin structure, and the organic silicon grafts to the polymer molecular chain, thus obtaining the organic silicon modified spiro-orthoester epoxy resin. -1 -1 -1 -1

[0029] 2. The organic silicon modified spiro-orthoester epoxy resin of the present application has extremely low stress shrinkage and good thermal stability, and also has excellent bonding performance and mechanical properties of the epoxy resin, and can meet the reliability requirements of special electronic packaging. BRIEF DESCRIPTION OF DRAWINGS

[0030] The present application is further described below in conjunction with the drawings and examples.

[0031] Figure 1 The present application is further described below in conjunction with the drawings and examples. DETAILED DESCRIPTION

[0032] In order to facilitate the understanding of those skilled in the art, the present application is further described below in conjunction with examples, and the content mentioned in the examples is not a limitation of the present application.

[0033] As used herein, "and / or" includes the term "and" and / or the term "or", and any combination thereof. The terms used herein are only used to describe specific embodiments, and are not intended to limit the present application. As used herein, the singular forms "a", "an", and "the" are also intended to include the plural forms, unless the context clearly indicates otherwise. It is further understood that "comprising" is used in the present specification to specify the stated features, integers, steps, operations, elements, and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or combinations thereof.

[0034] ​​​​Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0035] The exemplary applications described herein can suitably lack any one or more of the elements described herein, and thus, should not be necessarily construed as requiring all of the components or steps described. The terms "comprise", "include", "contain", "have" and the like, are to be construed in an open, non-limiting sense, and are intended to be construed as "including, but not limited to". Additionally, the term "consisting essentially of will be used as a descriptive term, not a limiting term, and the use of such term is not intended to exclude any equivalent to the features described, but only to describe some of the features of the application. Thus, although the application has been specifically disclosed by preferred embodiments and optional features, modification of the application excluding any of the features described can occur to persons skilled in the art within the scope of the application, and such modifications are intended to be within the scope of the application.

[0036] The raw materials or reagents used in the examples and comparative examples of the present application are purchased from mainstream manufacturers in the market. If the manufacturer is not specified or the concentration is not specified, it is an analytical pure raw material or reagent that can be obtained conventionally, and there is no particular limitation as long as it can play the expected role. The reaction kettle and rotary evaporator and other instruments and equipment used in the examples are purchased from major manufacturers in the market, as long as they can play the expected role, and there is no particular limitation. If the specific technology or condition is not specified in the examples, it is carried out according to the technology or condition described in the literature in the art or according to the product instruction.

[0037] The first object of the present application provides a silicone-modified spiro ortho ester epoxy resin, which comprises the following raw materials in terms of moles:

[0038] Epoxy resin 1 mol

[0039] Silicone crosslinking agent 2.0-2.1 mol

[0040] Aminated spiro ortho ester 1.1-1.2 mol.

[0041] In one embodiment, the epoxy resin is a hydrogenated bisphenol A epoxy resin, which can be a hydrogenated bisphenol A epoxy resin with CAS: 30583-72-3.

[0042] In one embodiment, the silicone crosslinking agent is isocyanate propyl trimethoxysilane, CAS: 15396-00-6.

[0043] In one embodiment, the amino spiro-ortho ester is prepared by reacting the spiro-ortho ester with ammonia gas in the presence of a catalyst.

[0044] In one embodiment, the catalyst is alumina; the catalyst is used in an amount of 0.005-0.01 times the moles of the spiro-ortho ester.

[0045] In one embodiment, the method for preparing the spiro-ortho ester comprises the following steps:

[0046] After reacting dipentaerythritol (25.4 g, 0.1 mol), di-n-butyl tin oxide (26.6 g, 0.1 mol) and toluene (200 ml), carbon disulfide (10 ml) is added to continue the reaction; after the reaction is completed, post-treatment is performed to obtain the spiro-ortho ester.

[0047] Specifically, the method for preparing the spiro-ortho ester comprises the following steps: dipentaerythritol, di-n-butyl tin oxide and toluene are added to a three-necked flask, stirred and refluxed for 15 h, CS2 is added dropwise after the reaction solution is cooled to room temperature, then slowly heated to 90-110 °C for 15 h, low-boiling-point components are removed by distillation under reduced pressure, the obtained viscous liquid is washed with D40 cleaning agent (ExxonMobil hydrocarbon), recrystallized with toluene, and the spiro-ortho ester is obtained.

[0048] The second object of the present application provides a method for preparing a silicone-modified spiro-ortho ester epoxy resin, comprising the following steps:

[0049] 1) Amino modification of the spiro-ortho ester

[0050] The spiro-ortho ester is reacted with ammonia gas in the presence of a catalyst at 100-110 °C for 3-4 h. After the reaction is completed, the amino spiro-ortho ester is obtained.

[0051] 2) Preparation of the spiro-ortho ester modified epoxy resin

[0052] After mixing the epoxy resin and the amino spiro-ortho ester, the mixture is reacted at 60-70 °C for 12-16 h; after the reaction is completed, the spiro-ortho ester modified epoxy resin is obtained.

[0053] 3) Silicone modification

[0054] The spiro-ortho ester modified epoxy resin is reacted with a silicone crosslinking agent, and after the reaction is completed, the silicone-modified spiro-ortho ester epoxy resin is obtained.

[0055] Synthetic experimental scheme:

[0056] Specifically, the method for preparing the silicone-modified spiro-ortho ester epoxy resin comprises the following synthetic route:

[0057]

[0058] Specific synthesis experimental scheme:

[0059] Spirocyclic ester amination modification:

[0060] Dissolve 0.1 mol of spirocyclic ester compound in 300 ml of toluene, add 0.2 g of AI2O3 as catalyst, heat to 80-100°C, and pass in ammonia gas for 12 h, and then distill under reduced pressure to obtain the aminated spirocyclic ester compound.

[0061] Synthesis of spirocyclic ester modified epoxy resin:

[0062] Add part of the aminated modified spirocyclic ester compound to hydrogenated bisphenol A epoxy resin, control the temperature at 100-110°C, and stir for 3 h to prepare spirocyclic ester modified hydrogenated bisphenol A epoxy resin by ring opening reaction of primary amine and epoxy group.

[0063] Synthesis of silicone modified spirocyclic ester epoxy resin:

[0064] Add 3-isocyanate propyl trimethoxysilane in the above reaction, control the temperature at 60-70°C, and stir for 12 h to graft the silicone structure onto the epoxy resin structure by reaction of isocyanate and alcohol hydroxyl group, thereby obtaining modified epoxy resin with organosiloxane structure.

[0065] Determination of chemical reactions in the above synthesis process:

[0066] Equipment: Fourier infrared spectrometer

[0067] Test results: ①The test results of infrared spectrum of spirocyclic ester synthesis product show that the main absorption peak at 1100 cm -1 is weakened, the alcohol hydroxyl absorption peak near 3300 cm -1 is weakened, and the spirocyclic characteristic peak at 1230 cm -1 appears, proving the generation of spirocyclic ester monomer.

[0068] ②The test results of infrared spectrum of spirocyclic ester amination synthesis product show that the alcohol hydroxyl absorption peak near 3300 cm -1 is basically disappeared, and a new absorption peak at 1600 cm -1 appears, indicating that the amino group replaces the original alcohol hydroxyl structure to generate amino modified spirocyclic compound.

[0069] ③The test results of infrared spectrum of spirocyclic ester modified epoxy resin synthesis product show that the epoxy characteristic functional group at 913 cm -1 is disappeared, and the alcohol hydroxyl absorption peak at 3300 cm -1The new absorption peak near the alcohol hydroxyl group appeared, which proved that the amino group and the ring opening reaction of the epoxy group were completed.

[0070] The infrared spectrum data of the synthesis product of the organosilicon modified spiro-orthoester epoxy resin showed that the absorption peak of 2200 cm -1 The absorption peak of the isocyanate near the alcohol hydroxyl group disappeared, 1700 cm -1 , 1530 cm -1 , 3200 cm -1 The absorption peak of the polyurethane structure appeared, which proved that the isocyanate structure and the alcohol hydroxyl group in the spiro modified epoxy resin structure reacted, and the organosilicon grafting reaction was on the polymer molecular chain, and the organosilicon modified spiro-orthoester epoxy resin was obtained.

[0071] The third object of the present application is to apply the organosilicon modified spiro-orthoester epoxy resin to an adhesive.

[0072] Specifically, the organosilicon modified spiro-orthoester epoxy resin can be prepared into an adhesive according to the raw material composition of the component A component and the component B component as shown in Table 1; in the preparation method, that is, according to the specific weight part composition of the component A component, the materials are prepared, and are fully mixed to obtain the component A component; the component B component is prepared according to the specific weight part.

[0073] Table 1

[0074]

[0075] The adhesive prepared in Table 1 is subjected to the following performance tests, and the specific test results are summarized in Table 2; the performance test method is as follows:

[0076] ① Thermal decomposition temperature (℃): thermal gravimetric analyzer (TGA), thermal analysis equipment (model: TG209(f3), Germany NETZSCH company), heating rate: 10℃ / min, temperature range: 0℃-800℃.

[0077] ② Thermal expansion coefficient (ppm / ℃): static thermal mechanical analyzer (TMA), thermal analysis equipment (model: TMA450, USA TA company), heating rate 10℃ / min, temperature range: -30℃-230℃.

[0078] ③ Shear strength / tensile strength (Mpa), 25℃: universal tensile testing machine, GB / T7124-2008.

[0079] Table 2

[0080]

[0081] From Table 2, it can be seen that the organic silicon modified spiro-orthoester epoxy resin of the application has very low stress shrinkage and good thermal stability, and at the same time has excellent bonding properties and mechanical properties of epoxy resin. When applied to prepare adhesives, it has a high thermal decomposition temperature, a low thermal expansion coefficient, and a very high shear strength and tensile strength, which can meet the reliability requirements of special electronic packaging.

[0082] Comparative Example 1 has a lower thermal decomposition temperature, a larger thermal expansion coefficient, and lower shear strength and tensile strength than Examples 1 and 2, indicating that the organic silicon modified spiro-orthoester epoxy resin can increase the heat resistance of the system, reduce the thermal expansion coefficient, and increase the bonding strength and bulk strength.

[0083] Comparative Example 2 has a lower thermal decomposition temperature, a larger thermal expansion coefficient, and lower shear strength and tensile strength than Examples 1 and 3, indicating that the organic silicon modified spiro-orthoester epoxy resin can increase the heat resistance of the system, reduce the thermal expansion coefficient, and increase the bonding strength and bulk strength.

[0084] Comparative Example 3 has a lower thermal decomposition temperature, a larger thermal expansion coefficient, and lower shear strength and tensile strength than Examples 1 and 4, indicating that the organic silicon modified spiro-orthoester epoxy resin can increase the heat resistance of the system, reduce the thermal expansion coefficient, and increase the bonding strength and bulk strength.

[0085] The above examples are preferred implementation schemes of the application. In addition to this, the application can also be implemented in other ways, and any obvious substitutions without departing from the concept of the application are within the protection scope of the application.

Claims

1. A silicone-modified spiro-ortho-ester epoxy resin characterized in that, consists of the following raw materials in terms of moles: epoxy resin 1 mol silicone crosslinking agent 2.0-2.1 mol amino-modified spiro-orthoester 1.1-1.2 mol the epoxy resin is hydrogenated bisphenol A epoxy resin; the silicone crosslinking agent is isocyanate propyl trimethoxysilane; the preparation method of the silicone-modified spiro-orthoester epoxy resin comprises the following steps: after mixing the epoxy resin and the amino-modified spiro-orthoester, reaction is carried out; after the reaction is completed, a spiro-orthoester-modified epoxy resin is obtained; the spiro-orthoester-modified epoxy resin and the silicone crosslinking agent are mixed and reacted, and after the reaction is completed, a silicone-modified spiro-orthoester epoxy resin is obtained.

2. The silicone-modified spiro-orthoester epoxy resin of claim 1, wherein the amino-modified spiro-orthoester is obtained by reacting a spiro-orthoester with ammonia gas under the action of a catalyst.

3. The silicone-modified spiro-orthoester epoxy resin of claim 2, wherein, the catalyst is alumina; the amount of the catalyst is 0.005-0.01 times the moles of the spiro-orthoester.

4. The silicone-modified spiro-orthoester epoxy resin of claim 2, wherein the preparation method of the spiro-orthoester comprises the following steps: after the di-n-butyl tin oxide and toluene are reacted, carbon disulfide is added for further reaction; after the reaction is completed, post-treatment is carried out, and a spiro-orthoester is obtained.

5. The method of making a silicone-modified spiro-orthoester epoxy resin according to any one of claims 1-4, characterized in that, comprises the following steps: 1) amino-modification of the spiro-orthoester the amino-modified spiro-orthoester is obtained by reacting a spiro-orthoester with ammonia gas under the action of a catalyst; 2) preparation of a spiro-orthoester-modified epoxy resin after mixing the epoxy resin and the amino-modified spiro-orthoester, reaction is carried out; after the reaction is completed, a spiro-orthoester-modified epoxy resin is obtained; 3) silicone modification the spiro-orthoester-modified epoxy resin and the silicone crosslinking agent are mixed and reacted, and after the reaction is completed, a silicone-modified spiro-orthoester epoxy resin is obtained.

6. The production method according to claim 5, wherein in step 2), the reaction conditions are 100-110°C for 3-4h.

7. The preparation method according to claim 5, characterized in that, in step 3), the reaction conditions are 60-70°C for 12-16h.

8. Use of a silicone-modified spiro-ortho-ester epoxy resin, characterized in that the silicone-modified spiro-orthoester epoxy resin of any one of claims 1-4 or the silicone-modified spiro-orthoester epoxy resin prepared by the preparation method of any one of claims 5-7 is applied to an adhesive.

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