Preparation method of silane modified epoxy resin

Abstract

The invention provides a preparation method of silane modified epoxy resin, which comprises the following steps: under the protection of nitrogen, adding 10-50 parts by weight of epoxy resin and 40-60 parts by weight of organosilane containing secondary amine groups into a reaction kettle, heating to 50-60 DEG C under a stirring condition, and reacting for 1-5 hours; adding 10-50 parts by weight of organic silane containing isocyanate functional groups within 1 hour, continuously heating to 70-80 DEG C, and reacting for 1-5 hours; cooling to room temperature and filtering to obtain a target product. By introducing organosilane containing a secondary amine group and organosilane containing an isocyanate functional group, an efficient end-capping reaction of epoxy resin is realized, a modified product of which the molecular structure simultaneously contains an epoxy group, a phenyl group, a carbamate bond and a silane alkoxy group is obtained, the crosslinking sites of the epoxy resin are increased, and the crosslinking property of the epoxy resin is improved. And silane groups acting with a plurality of substrates are introduced, so that the adhesive property on materials such as PC, PET, PBT, PPS, PMMA and PA6 is obviously improved.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resins, and in particular to a method for preparing a silane-modified epoxy resin. Background Art

[0002] Traditional epoxy resins are widely used in coatings, adhesives, and electronic packaging materials due to their excellent mechanical, chemical, and electrical properties. However, their poor adhesion to some plastic substrates, such as PC, PET, PBT, PPS, PMMA, and PA6, limits their further application. To enhance the adhesive properties of epoxy resins, attempts have been made to modify them with silicones. Summary of the Invention

[0003] The present invention aims to disclose a method for preparing a silane-modified epoxy resin. The method has a mild process and a stable product. By introducing an organosilane containing a secondary amine group and an organosilane containing an isocyanate functional group, an efficient end-capping reaction of the epoxy resin is achieved, and a modified product containing epoxy groups, phenyl groups, urethane bonds and silane alkoxy groups in the molecular structure is obtained. Not only are the cross-linking sites of the epoxy resin increased, but silane groups that can interact with various substrates are also introduced. The method significantly improves the bonding performance of materials such as PC, PET, PBT, PPS, PMMA, and PA6, effectively improving the bonding performance and cross-linking density of the materials. The method has stable viscosity, a long shelf life, good adaptability, and is suitable for industrial applications of adhesive systems.

[0004] To achieve the above object, the present invention provides a method for preparing a silane-modified epoxy resin, comprising the following steps:

[0005] Step 1: Under nitrogen protection, add 10-50 parts by weight of epoxy resin and 40-60 parts by weight of organosilane containing secondary amine groups into a reaction kettle, raise the temperature to 50-60° C. under stirring, and react for 1-5 hours;

[0006] Step 2: Add 10 to 50 parts by weight of an isocyanate-functional organosilane within 1 hour, continue heating to 70 to 80° C., and react for 1 to 5 hours;

[0007] Step 3: Cool to room temperature and filter to obtain the target product.

[0008] In some embodiments, the epoxy resin structural formula in step 1 is:

[0009]

[0010] Wherein, R1 is a methyl group or a hydrogen atom.

[0011] In some embodiments, the epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol A / F epoxy resin, and has an epoxy equivalent weight of 100 to 500 g / eq.

[0012] In some embodiments, the epoxy resin is DER TM 331 epoxy resin (Olin) epoxy equivalent 182 ~ 192g / eq, DER TM 383 epoxy resin (Olin) epoxy equivalent 176 ~ 183g / eq, DER TM 354 epoxy resin (Olin) epoxy equivalent 167 ~ 174g / eq, DER TM One of 356 epoxy resin (Olin) with epoxy equivalent of 176-184 g / eq, NPEL128 epoxy resin (Nan Ya Plastics) with epoxy equivalent of 184-190 g / eq, and NPEL127 epoxy resin (Nan Ya Plastics) with epoxy equivalent of 176-184 g / eq.

[0013] In some embodiments, the structural formula of the organosilane containing a secondary amine group in step 1 is:

[0014]

[0015] Wherein, n=1-10; R2 is n-butyl, trimethoxysilylpropyl, triethoxysilylpropyl or phenyl; R3, R4 and R5 are all alkoxy or at least one of them is alkyl, the alkoxy is methoxy, ethoxy, isopropoxy or butoxy, and the alkyl is methyl or ethyl.

[0016] In some embodiments, the organosilane containing a secondary amine group is one or more of n-butylaminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(N-anilino)propyltriethoxysilane, bis(trimethoxysilylpropyl)amine, and bis[3-(triethoxysilyl)propyl]amine.

[0017] In some embodiments, the isocyanate-functional organosilane in step 2 has the structural formula:

[0018]

[0019] Wherein, o=1-10; R6, R7, R8 are all alkoxy groups or at least one of them is alkyl and the others are alkoxy groups, the alkoxy group is methoxy, ethoxy, isopropoxy or butoxy, and the alkyl group is methyl, ethyl or butyl.

[0020] In some embodiments, the isocyanate functional group-containing organosilane is one or more of isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, and isocyanatepropylmethyldimethoxysilane.

[0021] Compared with the prior art, the present invention has the following beneficial effects: a mild process and stable products; by introducing an organosilane containing a secondary amine group and an organosilane containing an isocyanate functional group, an efficient end-capping reaction of the epoxy resin is achieved, and a modified product containing epoxy groups, phenyl groups, carbamate bonds and silane alkoxy groups in the molecular structure is obtained. This not only increases the cross-linking sites of the epoxy resin, but also introduces silane groups that can interact with a variety of substrates, significantly improving the bonding performance of materials such as PC, PET, PBT, PPS, PMMA, and PA6, effectively improving the bonding performance and cross-linking density of the materials, having stable viscosity, a long storage period, and good adaptability, and being suitable for industrial applications of adhesive systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The figure is a formula diagram of the MS (silane modified polymer) glue of the present invention;

[0023] Figure 2 This is a diagram showing the bonding performance of the silane-modified epoxy resin provided by the present invention; DETAILED DESCRIPTION

[0024] The present invention is described in detail below with reference to the various embodiments shown in the accompanying drawings, but it should be noted that these embodiments are not limitations of the present invention, and any equivalent transformations or substitutions in functions, methods, or structures made by ordinary technicians in this field based on these embodiments are all within the scope of protection of the present invention.

[0025] Example 1

[0026] This embodiment discloses a method for preparing a silane-modified epoxy resin, which specifically comprises the following steps:

[0027] Step 1: Under nitrogen protection, 35.3 parts by weight of DER TM 331 epoxy resin (Olin) and 44.3 parts of n-butylaminopropyltrimethoxysilane were added to the reaction kettle.

[0028] Step 2: While stirring, heat to 60°C and react for 3 hours.

[0029] Step 3: Add 38.5 parts of isocyanatepropyltrimethoxysilane within 1 hour.

[0030] Step 4: After adding, heat to 70°C and react for 2 hours.

[0031] Step 5: Cool to room temperature and filter to obtain silicone-modified epoxy resin E1 with a viscosity of 3065 cP.

[0032] Example 2

[0033] The present embodiment discloses a method for preparing a silane-modified epoxy resin, which specifically comprises the following steps:

[0034] Step 1: Under nitrogen protection, 34 parts by weight of DER TM 383 epoxy resin (Olin) and 44.3 parts of n-butylaminopropyltrimethoxysilane were added to the reaction kettle.

[0035] Step 2: While stirring, heat to 60°C and react for 3 hours.

[0036] Step 3: Add 38.5 parts of isocyanatepropyltrimethoxysilane within 1 hour.

[0037] Step 4: After adding, heat to 70°C and react for 2 hours.

[0038] Step 5: Cool to room temperature and filter to obtain silicone-modified epoxy resin E2 with a viscosity of 2700 cP.

[0039] Example 3

[0040] The present embodiment discloses a method for preparing a silane-modified epoxy resin, which specifically comprises the following steps:

[0041] Step 1: Under nitrogen protection, 35.3 parts by weight of DER TM 331 epoxy resin (Olin) and 63.4 parts of bis(3-trimethoxysilylpropyl)amine were added to the reaction kettle.

[0042] Step 2: While stirring, heat to 60°C and react for 3 hours.

[0043] Step 3: Add 38.5 parts of isocyanatepropyltrimethoxysilane within 1 hour.

[0044] Step 4: After adding, heat to 70°C and react for 2 hours.

[0045] Step 5: Cool to room temperature and filter to obtain silicone-modified epoxy resin E3 with a viscosity of 4500 cP.

[0046] like Figure 1Shown are three adhesion promoters (E1, E2, and E3) synthesized at 0.5% each added to a typical MS (silane-modified polymer) adhesive formulation to create a single-component adhesive. MS-E0: Basic comparison formulation without adhesion promoter. MS-E1, MS-E2, and MS-E3: 0.5% E1, 0.5% E2, and 0.5% E3 added, respectively.

[0047] like Figure 2 As shown, relative to the basic formula MS, the three synthetic adhesion promoters E1, E2, and E3 were added to the typical formula of MS (silane-modified polymer) glue at an addition amount of 0.5% respectively to prepare a single-component glue, which has better bonding effect with the substrate.

[0048] By introducing organosilanes containing secondary amine groups and organosilanes containing isocyanate functional groups, an efficient end-capping reaction of epoxy resins is achieved, and a modified product containing epoxy groups, phenyl groups, carbamate bonds and silane alkoxy groups in the molecular structure is obtained. This not only increases the cross-linking sites of the epoxy resin, but also introduces silane groups that can interact with a variety of substrates. The bonding performance of materials such as PC, PET, PBT, PPS, PMMA, and PA6 is significantly improved, and the bonding performance and cross-linking density of the materials are effectively improved. The viscosity is stable, the storage period is long, and the adaptability is good, making it suitable for industrial applications of adhesive systems.

[0049] The series of detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

[0050] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing a silane-modified epoxy resin, characterized in that: The steps include: Step 1: Under nitrogen protection, add 10-50 parts by weight of epoxy resin and 40-60 parts by weight of organosilane containing secondary amine groups into a reaction kettle, raise the temperature to 50-60° C. under stirring, and react for 1-5 hours; Step 2: Add 10 to 50 parts by weight of an isocyanate-functional organosilane within 1 hour, continue heating to 70 to 80° C., and react for 1 to 5 hours; Step 3: Cool to room temperature and filter to obtain the target product.

2. The method for preparing a silane-modified epoxy resin according to claim 1, wherein The epoxy resin structural formula in step 1 is: Wherein, R1 is a methyl group or a hydrogen atom.

3. The method for preparing a silane-modified epoxy resin according to claim 2, wherein The epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol A / F epoxy resin, and has an epoxy equivalent of 100 to 500 g / eq.

4. The method for preparing a silane-modified epoxy resin according to claim 3, wherein The epoxy resin is DER TM 331 epoxy resin (Olin) epoxy equivalent 182 ~ 192g / eq, DER TM 383 epoxy resin (Olin) epoxy equivalent 176 ~ 183g / eq, DER TM 354 epoxy resin (Olin) epoxy equivalent 167 ~ 174g / eq, DER TM One of 356 epoxy resin (Olin) with epoxy equivalent of 176-184 g / eq, NPEL128 epoxy resin (Nan Ya Plastics) with epoxy equivalent of 184-190 g / eq, and NPEL127 epoxy resin (Nan Ya Plastics) with epoxy equivalent of 176-184 g / eq.

5. The method for preparing a silane-modified epoxy resin according to claim 1, wherein The structural formula of the organosilane containing a secondary amine group in step 1 is: Wherein, n=1-10; R2 is n-butyl, trimethoxysilylpropyl, triethoxysilylpropyl or phenyl; R3, R4 and R5 are all alkoxy or at least one of them is alkyl, the alkoxy is methoxy, ethoxy, isopropoxy or butoxy, and the alkyl is methyl or ethyl.

6. The method for preparing a silane-modified epoxy resin according to claim 5, wherein The organosilane containing a secondary amine group is one or more of n-butylaminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(N-anilino)propyltriethoxysilane, bis(trimethoxysilylpropyl)amine, and bis[3-(triethoxysilyl)propyl]amine.

7. The method for preparing a silane-modified epoxy resin according to claim 1, wherein The structural formula of the organosilane containing isocyanate functional group in step 2 is: Wherein, o=1-10; R6, R7, R8 are all alkoxy groups or at least one of them is alkyl and the others are alkoxy groups, the alkoxy group is methoxy, ethoxy, isopropoxy or butoxy, and the alkyl group is methyl, ethyl or butyl.

8. The method for preparing a silane-modified epoxy resin according to claim 7, wherein: The isocyanate functional group-containing organosilane is one or more of isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, and isocyanatepropylmethyldimethoxysilane.

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