A silicone-modified epoxy spirocyclic resin, a preparation method and applications thereof

Abstract

The present application relates to the technical field of epoxy resin, and particularly relates to a kind of organic silicon modified epoxy spiro resin and preparation method and application.A kind of organic silicon modified epoxy spiro resin is disclosed in the present application, including the following raw materials by weight parts: bisphenol A epoxy resin 0.75-8 parts, 3-isocyanate group propyl trimethoxysilane 0.49-0.63 parts, 6-caprolactone 0.25-0.35 parts, catalyst 0.01-0.02 parts.The organic silicon modified epoxy spiro resin described in the present application has the excellent performance of organic silicon resin and epoxy resin, i.e., the curing shrinkage and stress of epoxy resin can be greatly reduced, and the adhesion and curing efficiency of the original epoxy resin can also be maintained, the volume shrinkage rate of epoxy structural adhesive can be effectively reduced, the internal stress and modulus of epoxy structural adhesive can be reduced, and the adhesion and glue elongation at break of epoxy structural adhesive can be greatly improved.

Description

TECHNICAL FIELD

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

[0002] Epoxy resin is a kind of polymer with crosslinked network structure, and because it has very high cost performance, good mechanical properties, chemical resistance, bonding performance, heat resistance and solvent resistance, meets green environmental protection conditions; It is widely used in plastic industry, paint industry, chemical industry, national defense and many other fields.However, due to the high crosslinked skeleton structure of pure epoxy resin, and the matrix material is brittle after curing, its cracking performance under acid corrosion condition, impact resistance is poor, which can not fully meet the requirements of the related chemical industry with high performance requirements.

[0003] Organic silicon resin is a polymer with silicon-oxygen bond as the main chain of molecule, compared with the common carbon-carbon bond as the main chain of molecule, it has higher bond energy, so it has better heat resistance, insulation performance, water resistance and weather resistance; Flexibility will be more excellent; But because its curing temperature is high and the curing time is long, the coating has poor resistance to organic solvents, and the adhesion is low, which greatly limits its wide application; Thus limiting its application.

[0004] Therefore, the present application provides an organic silicon modified epoxy spiro resin and preparation method and application. SUMMARY

[0005] In order to overcome the shortcomings of the prior art, the present application provides an organic silicon modified epoxy spiro resin and preparation method and application, which combines the excellent performance of organic silicon resin and epoxy resin, i.e.can greatly reduce the curing shrinkage and stress of epoxy resin, and also can maintain the adhesion and curing efficiency of the original epoxy resin, can effectively reduce the volume shrinkage rate of epoxy structural adhesive, reduce the internal stress and modulus of epoxy structural adhesive, can greatly improve the adhesion and glue elongation rate of epoxy structural adhesive, the organic silicon modified epoxy spiro resin added in the epoxy structural adhesive can be widely used as electronic packaging material and electronic adhesive material.

[0006] The technical solution 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 epoxy spiro resin, which comprises the following raw materials by weight:

[0008]

[0009] Preferably, the bisphenol A epoxy resin is any one of E-44 bisphenol A epoxy resin, E-12 bisphenol A epoxy resin.

[0010] Preferably, the catalyst is boron trifluoride etherate.

[0011] The second object of the present application provides a preparation method of the silicone-modified epoxy spiro resin, comprising the following steps:

[0012] The bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are mixed, and then a condensation reaction is performed to obtain the silicone-modified epoxy resin; the silicone-modified epoxy resin, 6-caprolactone and a catalyst are mixed, and then a condensation reaction is performed to obtain the silicone-modified epoxy spiro resin.

[0013] Preferably, the bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are mixed, and then an adjusting agent is added at 60-90 DEG C; and a condensation reaction is performed for 2-4 h.

[0014] Preferably, the adjusting agent is phosphoric acid.

[0015] Preferably, the silicone-modified epoxy resin, 6-caprolactone and a catalyst are mixed, and then a condensation reaction is performed at 60-90 DEG C for 2-4 h.

[0016] The second object of the present application provides the application of the silicone-modified epoxy spiro resin, which is applied to the preparation of structural glue and adhesive.

[0017] Preferably, the structural glue comprises the following raw materials in parts by weight:

[0018] Photothermal double-cured resin 30-50 parts, silicone-modified epoxy spiro resin 1.5-9 parts, epoxy diluent 20-25 parts, thermal curing agent 0.5-1 part, stabilizer 0.3-0.5 part, silane coupling agent 2-3 parts, photoinitiator 2-3 parts, and silicon powder 60-65 parts.

[0019] Preferably, the structural glue and adhesive are used as electronic packaging materials and / or electronic adhesive materials.

[0020] The present application has the following advantages:

[0021] 1. The silicone-modified epoxy spiro resin prepared by the present application has the excellent performance of both silicone resin and epoxy resin, and the two materials are complementary to each other, so that the shortcomings of the two materials can be made up, the flexibility of the silicone resin can greatly reduce the curing shrinkage and stress of the epoxy resin, and the adhesion and curing efficiency of the original epoxy resin can be maintained.

[0022] 2. The epoxy structural adhesive described in the application can effectively reduce the volume shrinkage rate of the epoxy structural adhesive, reduce the internal stress and modulus of the epoxy structural adhesive, and greatly improve the adhesion and glue elongation at break of the epoxy structural adhesive, and can be widely used as electronic packaging materials and electronic adhesive materials. BRIEF DESCRIPTION OF DRAWINGS

[0023] The application will be further described below in conjunction with the drawings and examples.

[0024] Figure 1 The synthetic route map of the preparation method of the organic silicon modified epoxy spiro resin described in the application. DETAILED DESCRIPTION

[0025] In order to facilitate the understanding of those skilled in the art, the application will be further described below in conjunction with examples, and the content mentioned in the embodiments is not a limitation of the application.

[0026] As used herein, "and / or" includes the term "and" and / or the term "or", all combinations of one and more associated terms. The terms used herein are only used to describe specific embodiments, and are not intended to limit the 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 this 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.

[0027] Unless otherwise defined, all terms used in this text (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art to which the application belongs. It is further understood that terms such as defined in a commonly used dictionary, interpreted in accordance with their meanings in the relevant field, and not in an idealized or overly formal sense, unless otherwise defined herein.

[0028] The exemplary application described herein can be appropriately absent any one or more of the elements not specifically disclosed herein. Therefore, the terms "comprising", "including", "containing", and the like should be understood broadly and non-restrictively. In addition, the terms used herein are used as description, not limitation, and it is not intended that the use of these terms excludes any equivalent characteristics, but only describes some characteristics thereof, but according to the right, various modifications are possible within the scope of the application. Therefore, although the application has been specifically disclosed by the preferred embodiments and optional features, modifications disclosed herein can be recorded to embody the variations of the application by those skilled in the art, and such modifications and variations will be considered within the scope of the application. Therefore, although the application has been specifically disclosed by the preferred embodiments and optional features, modifications disclosed herein can be recorded to embody the variations of the application by those skilled in the art, and such modifications and variations will be considered within the scope of the application.

[0029] 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, and there is no particular limitation as long as they can play the expected role. 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 field or according to the product instruction.

[0030] The present application provides a silicone-modified epoxy spiro resin, which comprises the following raw materials by weight:

[0031]

[0032] Further, the bisphenol A epoxy resin is E03 type bisphenol A epoxy resin (produced by Guangdong Wengjiang Reagent Chemical Co., Ltd.).

[0033] Further, the catalyst is boron trifluoride etherate.

[0034] It can be understood that the weight of the bisphenol A epoxy resin is 0.75-8 parts, and the specific parts include the minimum and maximum values of the range, and every value between the minimum and maximum values, and the specific examples include but are not limited to the following point values: 0.75 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts.

[0035] It can be understood that the weight of 6-hexanolactone is 0.25-0.35 parts, and the specific parts include the minimum and maximum values of the range, and every value between the minimum and maximum values, and the specific examples include but are not limited to the following point values: 0.25 parts, 0.26 parts, 0.27 parts, 0.30 parts, 0.34 parts, 0.35 parts.

[0036] It can be understood that the weight of the catalyst is 0.01-0.02 parts, and the specific parts include the minimum and maximum values of the range, and every value between the minimum and maximum values, and the specific examples include but are not limited to the following point values: 0.01 parts, 0.012 parts, 0.013 parts, 0.018 parts, 0.02 parts.

[0037] It can be understood that the weight of 3-isocyanate propyl trimethoxysilane is 0.49-0.63 parts, and the specific parts include the minimum and maximum values of the range, and every value between the minimum and maximum values, and the specific examples include but are not limited to the following point values: 0.49 parts, 0.52 parts, 0.55 parts, 0.58 parts, 0.62 parts, 0.63 parts.

[0038] More specifically, the preparation method of the organic silicon modified epoxy spiro resin comprises the following steps:

[0039] The bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are mixed, and then a condensation reaction is performed to obtain an organic silicon modified epoxy resin; the organic silicon modified epoxy resin and 6-caprolactone and a catalyst are mixed, and then a condensation reaction is performed to obtain an organic silicon modified epoxy spiro resin.

[0040] Further, the bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are mixed, and then an adjusting agent (0.1-0.2 parts of phosphoric acid) is added, and a condensation reaction is performed at 60-90°C for 2-4h.

[0041] Further, the organic silicon modified epoxy resin and 6-caprolactone and a catalyst are mixed, and then a condensation reaction is performed at 60-90°C for 2-4h.

[0042] Most specifically, the preparation method of the organic silicon modified epoxy spiro resin disclosed in the present application comprises the following steps:

[0043] 1. The synthetic route map as shown

[0044]

[0045] 2. Preparation method

[0046] 1) Epoxy resin organic silicon modification

[0047] The bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are added to a reaction kettle, and then phosphoric acid is added, and stirred uniformly, and heated to 75°C, and then a condensation reaction is performed for 3h to obtain a modified organic silicon modified epoxy resin.

[0048] 2) Organic silicon modified epoxy resin spirocyclization

[0049] The obtained organic silicon modified epoxy resin and 6-caprolactone are added to a reaction kettle, and then dichloromethane is added for dilution, and stirred uniformly, and heated to 75°C, and then boron trifluoride ether is added as a catalyst, and a condensation reaction is performed for 4h to obtain a spirocyclized organic silicon modified epoxy resin, and finally an alkali washing treatment is performed to remove excess chloride ions, and the organic silicon modified epoxy spiro resin is obtained after drying.

[0050] In examples 1-3, the preparation method described above is used for preparation, and the raw material composition is shown in the following table:

[0051]

[0052]

[0053] The silicone-modified epoxy spiro resin prepared in Example 1-Example 3 was subjected to infrared performance characterization, and the results showed that:

[0054] The prepared silicone-modified epoxy resin was subjected to infrared spectrum detection, and the data showed that the isocyanate absorption peak near 2200 cm -1 disappeared, 1700 cm -1 , 1530 cm -1 , 3200 cm -1 appeared the absorption peak of polyurethane structure, indicating that the isocyanate structure and the alcohol hydroxyl group in the spiro-modified epoxy resin structure reacted, proving that the silicone grafting reaction onto the polymer molecular chain, obtaining the silicone-modified epoxy resin.

[0055] The prepared silicone-modified epoxy spiro resin was subjected to infrared spectrum detection, and the test results showed that the epoxy characteristic functional group disappeared at 913 cm -1 , which was due to the double ring-opening reaction; the epoxy group was simultaneously opened with 6-caprolactone and then reacted, and the epoxy group disappeared; at the same time, the chain ether bond absorption peak appeared at 1060 cm -1 and 1250 cm -1 ; further proving that the 6-caprolactone ring-opening was successful, and the double ring-opening reaction with the epoxy functional group formed the silicone-modified epoxy spiro resin.

[0056] In order to provide electronic packaging materials, electronic adhesive materials, the present application provides an epoxy structural adhesive, including the following raw materials by weight:

[0057] Photo-thermal dual-curing resin 30-50 parts, silicone-modified epoxy spiro resin 10-30 parts, epoxy diluent 20-25 parts, thermal curing agent 0.5-1 part, stabilizer 0.3-0.5 part, silane coupling agent 2-3 parts, photo initiator 2-3 parts, silicon powder 60-65 parts.

[0058] Specifically, the epoxy structural adhesive described in the present application includes the following raw materials by weight:

[0059] Photo-thermal dual-curing resin 30-50 parts, silicone-modified epoxy spiro resin 10-30 parts, epoxy diluent 20-25 parts, thermal curing agent 0.5-1 part, stabilizer 0.3-0.5 part, silane coupling agent 2-3 parts, photo initiator 2-3 parts, silicon powder 60-65 parts.

[0060] It can be understood that the photo-thermal dual-curing resin combines the two curing methods of photo-curing and thermal curing, thereby having more excellent curing effect and performance. The photo-thermal dual-curing resin in the application example is the aliphatic epoxy resin 2021P of Japan Daicel.

[0061] The epoxy diluent is mainly used to improve the process performance of the epoxy resin coating or adhesive, reduce the viscosity, increase the flowability, and improve the crosslinking strength. The epoxy diluent is selected from one or two of ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and o-tolyl glycidyl ether; the epoxy diluent in the application example of the present application is selected from ethylene glycol diglycidyl ether.

[0062] The thermal curing agent is a substance capable of initiating polymerization at a certain temperature. Common thermal curing agents include peroxides, organic acid anhydes, and amine compounds. These curing agents react with active groups in the epoxy resin to form a three-dimensional network structure, thereby achieving curing. The thermal curing agent in the application example of the present application is selected from the ammonium-closed Lewis salt Vicbase TC3632 produced by Shenzhen Kaiji.

[0063] The stabilizer is mainly used to improve the stability and long-term storage performance of the product. The corresponding stabilizer is added according to the reaction type of the glue curing agent. The stabilizer in the application example of the present application is selected from barbituric acid.

[0064] The silane coupling agent is an organosilicon compound with functional groups such as epoxy, hydroxyl, and amino groups in its chemical structure, thus having good thermal stability and weather resistance, as well as excellent electrical and mechanical properties. The silane coupling agent can be selected from any one of vinyl silane, amino silane, and methacryloyloxy silane. The silane coupling agent in the application example of the present application is selected from γ-glycidyl ether oxypropyl trimethoxysilane.

[0065] The photoinitiator is mainly used in photopolymerization, generating free radicals or ions by absorbing light energy to initiate polymerization or crosslinking reaction. Common photoinitiators include benzoin and its derivatives, benzoin ethers, alkylbenzophenone, acyl phosphine oxide, and benzophenone, etc. For example, the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 2-isopropylthioxanthone, and diaryliodonium salt. The initiator in the specific embodiment is 1-hydroxycyclohexyl phenyl ketone.

[0066] The silicon micro powder is a micro powder of silicon dioxide. In the application, the particle size of the silicon micro powder is 5-7 μm.

[0067] In the present application, the organosilicon modified epoxy spiro resin is applied to the following application examples to illustrate the performance of the epoxy structural adhesive:

[0068] Application Example 1

[0069] An epoxy structural adhesive, including the following raw materials by weight:

[0070] Photo-thermal dual-curing resin 30 parts, bisphenol A epoxy resin 30 parts, epoxy diluent 20 parts, thermal curing agent 0.5 parts, stabilizer 0.3 parts, silane coupling agent 2 parts, photo initiator 2 parts, silicon micro powder 60 parts.

[0071] Application Example 2

[0072] An epoxy structural adhesive, by weight parts, comprises the following raw materials:

[0073] Photo-thermal dual-curing resin 30 parts, bisphenol A epoxy resin 25 parts, silicone modified epoxy spiro resin 5 parts, epoxy diluent 20 parts, thermal curing agent 0.5 parts, stabilizer 0.3 parts, silane coupling agent 2 parts, photo initiator 2 parts, silicon micro powder 60 parts.

[0074] Application Example 3

[0075] An epoxy structural adhesive, by weight parts, comprises the following raw materials:

[0076] Photo-thermal dual-curing resin 30 parts, bisphenol A epoxy resin 20 parts, silicone modified epoxy spiro resin 10 parts, epoxy diluent 20 parts, thermal curing agent 0.5 parts, stabilizer 0.3 parts, silane coupling agent 2 parts, photo initiator 2 parts, silicon micro powder 60 parts.

[0077] Application Example 4

[0078] An epoxy structural adhesive, by weight parts, comprises the following raw materials:

[0079] Photo-thermal dual-curing resin 30 parts, bisphenol A epoxy resin 10 parts, silicone modified epoxy spiro resin 20 parts, epoxy diluent 20 parts, thermal curing agent 0.5 parts, stabilizer 0.3 parts, silane coupling agent 2 parts, photo initiator 2 parts, silicon micro powder 60 parts.

[0080] Application Example 5

[0081] An epoxy structural adhesive, by weight parts, comprises the following raw materials:

[0082] Photo-thermal dual-curing resin 30 parts, silicone modified epoxy spiro resin 30 parts, epoxy diluent 20 parts, thermal curing agent 0.5 parts, stabilizer 0.3 parts, silane coupling agent 2 parts, photo initiator 2 parts, silicon micro powder 60 parts.

[0083] The bisphenol A epoxy resin in application examples 1-5 is bisphenol A epoxy resin E03.

[0084] The structural adhesives prepared in application examples 1-5 are tested for performance, and the detection items include bonding strength, tensile strength, modulus, elongation at break, thermal expansion coefficient, glass transition temperature (TG), and the relevant detection results are summarized in Table 1.

[0085] Test method:

[0086] Adhesion strength: universal tensile testing machine, GB / T 7124-2008 Substrate: stainless steel-stainless steel Tensile strength / elongation at break: universal tensile testing machine, GB / T 1040.1-2018

[0087] Coefficient of thermal expansion / glass transition temperature: static thermal mechanical analyzer (TMA 450, TA Instruments), GB / T 4339-2008

[0088] Elastic modulus: dynamic mechanical analyzer (DMA), GB / T 40396-2021

[0089] Table 1

[0090]

[0091] From Table 1 and the specific raw material weight parts composition in Application Examples 1-5, it can be seen that in the structural adhesive, after introducing the silicone-modified epoxy spiro resin, the adhesive strength of the structural adhesive is improved, the elongation at break is also improved, and the bulk tensile strength is reduced. Preliminary analysis is that the silicone-modified epoxy spiro resin introduces relatively soft silicone and spiro ring compared with epoxy resin, which reduces the volume shrinkage rate during polymerization, thereby reducing the polymerization strength, and accordingly reducing the internal stress generated by violent reaction, so the adhesive strength can be improved.

[0092] At the same time, because of the silicone-modified epoxy spiro resin, the introduction of the relatively soft chain segment of silicone and spiro ring reduces the hardness of the adhesive, and the glass transition temperature also decreases accordingly, and the coefficient of thermal expansion also increases. However, the modulus decreases significantly, which also confirms the reason for the decrease in the bulk strength of the adhesive. The adhesive reduces the internal stress and reduces the volume shrinkage. As for the increase in the coefficient of thermal expansion, it can be further reduced by adjusting the formula, such as increasing the powder addition amount to further reduce the coefficient of thermal expansion, which can improve the thermal change performance.

[0093] Therefore, the epoxy structural adhesive prepared by the application examples 2-5 can effectively reduce the volume shrinkage rate of the adhesive, reduce the internal stress and modulus of the adhesive, and greatly improve the adhesion and elongation at break of the adhesive, which can be used as an electronic packaging material and electronic adhesive material.

[0094] The above embodiments are the preferred implementation of the present application. In addition to this, the present application can also be implemented in other ways, and any obvious substitutions within the concept of the present application are within the protection scope of the present application.

Claims

1. A structural adhesive, characterized in that, The following raw materials are included by weight parts: photothermal double solid resin 30-50 parts, silicone modified epoxy spiro resin 10-30 parts, epoxy diluent 20-25 parts, thermal curing agent 0.5-1 part, stabilizer 0.3-0.5 part, silane coupling agent 2-3 parts, photoinitiator 2-3 parts, silicon powder 60-65 parts; The silicone modified epoxy spiro resin includes the following raw materials by weight parts: The preparation method of the silicone modified epoxy spiro resin includes the following steps: The bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are mixed, then a condensation reaction is carried out to obtain a silicone modified epoxy resin; the silicone modified epoxy resin and 6-caprolactone, a catalyst are mixed, then a condensation reaction is carried out to obtain a silicone modified epoxy spiro resin.

2. The structural adhesive of claim 1, wherein The bisphenol A epoxy resin is any one of E-44 bisphenol A epoxy resin and E-12 bisphenol A epoxy resin.

3. The structural adhesive of claim 1, wherein The catalyst is boron trifluoride etherate.

4. The structural adhesive of claim 1, wherein The bisphenol A epoxy resin and 3-isocyanate propyl trimethoxysilane are mixed, then an adjusting agent is added, and a condensation reaction is carried out at 60-90°C for 2-4h.

5. The structural adhesive of claim 4, wherein The adjusting agent is phosphoric acid.

6. The structural adhesive of claim 1, wherein The silicone modified epoxy resin and 6-caprolactone, a catalyst are mixed, then a condensation reaction is carried out at 60-90°C for 2-4h.

7. The structural adhesive of claim 1, wherein The structural adhesive is used as electronic packaging material and / or electronic adhesive material.

Images