Tetraglycidyl amine-containing epoxy resin composition as well as preparation method and application thereof

Abstract

The invention provides a tetraglycidyl amine-containing epoxy resin composition as well as a preparation method and application thereof, and relates to the technical field of epoxy resin materials. The composition is prepared from the following raw materials in parts by weight: 40 to 60 parts of tetraglycidyl amine epoxy resin, 15 to 25 parts of novolac epoxy resin, 10 to 20 parts of diglycidyl phthalate, 15 to 30 parts of methylhexahydrophthalic anhydride, 10 to 20 parts of diethyltoluenediamine, 1 to 3 parts of a stabilizer, 8 to 16 parts of a toughening agent, 1 to 2.2 parts of a silane coupling agent and 3 to 7 parts of filler. Alkali liquor is dropwise added for several times, so that the tetraglycidyl amine epoxy resin has lower viscosity; the tetraglycidyl amine epoxy resin is mixed with the novolac epoxy resin and the diglycidyl phthalate, and under the interaction of the methylhexahydrophthalic anhydride, the diethyltoluenediamine, the flexibilizer and other auxiliaries, a composition product with excellent mechanical properties, electrical properties and stability is obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of epoxy resin materials, and particularly relates to a composition containing tetraglycidyl amine epoxy resin and a preparation method and application thereof. BACKGROUND

[0002] Epoxy resin is a high molecular polymer containing two or more than two epoxy groups, which can cross-link with a curing agent to form a three-dimensional network structure. The epoxy resin and the curing agent are combined in proportion to form an adhesive, and the obtained epoxy resin adhesive has stable chemical properties, such as acid and alkali resistance, corrosion resistance, high bonding strength, and electrical insulation, and is widely used in the fields of construction, machinery, electronics, electrical appliances, and aerospace. However, the glass transition temperature of general epoxy resin is 100-160℃, and the thermal deformation temperature is 70-140℃, which cannot meet the requirements of high-temperature-resistant occasions such as aerospace electromechanical devices.

[0003] Multi-functional epoxy resins (such as tetraglycidyl-4,4'-diamino diphenyl methane, tetraglycidyl-4,4'-diamino diphenyl ether, tetraglycidyl-3,4'-diamino diphenyl ether, etc.) have multiple epoxy groups in their molecular structure, and the cured product has high cross-linking density, high glass transition temperature (Tg), and a thermal deformation temperature greater than 200℃, so it can be used for long periods above 160℃. However, the viscosity of these resins on the market is large, which brings many inconveniences to actual use. In addition, if glycidyl amine is used alone or in an unreasonable amount as an epoxy resin component, not only will the composition increase, but also the brittleness of the product will increase, which is easy to cause cracking.

[0004] Chinese invention patent CN118852064A discloses a trisglycidyl 4-amino-3-methyl phenol epoxy resin and its preparation method and application. The prepared trisglycidyl 4-amino-3-methyl phenol epoxy resin, as a kind of adhesive component, has a relatively optimal mechanical strength and a high Tg value after curing, but the improvement effect is limited.

[0005] The Chinese invention patent CN115232585A discloses a moisture and hydrolysis resistant single-component epoxy resin composition and its preparation method and application. The composition includes the following raw materials in parts by weight: epoxy resin 40-60 parts, thiol compound 20-60 parts, curing accelerator 0.5-10 parts, stabilizer 0.1-5 parts, silane coupling agent 0.1-5 parts, and filler 0.1-40 parts. The invention uses thiol compounds as the curing agent of epoxy resin to improve moisture resistance and crosslinking strength. However, the improvement of the mechanical properties and thermal stability of the multi-thiol compound with a specific structure on the epoxy resin is limited to the multi-thiol curing agent containing ester bonds. The glass transition temperature of the final multi-functional epoxy resin mixture product is only 110-120℃, and the mechanical properties and thermal stability are not significantly improved.

[0006] Therefore, further research is needed on the components of epoxy resin and curing agent, toughening agent, etc. Under the premise of reducing the viscosity of multi-functional epoxy resin, the components interact with each other to make the bonding strength of epoxy resin high, further improving the mechanical properties, electrical properties, and stability of the epoxy resin composition. SUMMARY

[0007] The present application provides a composition containing tetraglycidyl amine epoxy resin and its preparation method and application to solve the problems in the prior art. By preparing tetraglycidyl amine epoxy resin with low viscosity, mixing with phenolic epoxy resin and phthalic acid diglycidyl ester, and interacting with methyl hexahydrophthalic anhydride, diethyl toluene diamine, toughening agent and other additives, a composition product with excellent mechanical, electrical and stability properties is formed.

[0008] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: Firstly, the present application provides a composition containing tetraglycidyl amine epoxy resin. The raw materials include, in parts by weight: 40-60 parts of tetraglycidyl amine epoxy resin, 15-25 parts of phenolic epoxy resin, 10-20 parts of phthalic acid diglycidyl ester, 15-30 parts of methyl hexahydrophthalic anhydride, 10-20 parts of diethyl toluene diamine, 1-3 parts of stabilizer, 8-16 parts of toughening agent, 1-2.2 parts of silane coupling agent, and 3-7 parts of filler.

[0009] Preferably, the composition includes, in parts by weight: 45-55 parts of tetraglycidyl amine epoxy resin, 18-22 parts of phenolic epoxy resin, 13-18 parts of phthalic acid diglycidyl ester, 20-26 parts of methyl hexahydrophthalic anhydride, 13-18 parts of diethyl toluene diamine, 1.5-2.5 parts of stabilizer, 10-13 parts of toughening agent, 1.3-2 parts of silane coupling agent, and 5-6 parts of filler.

[0010] Further preferably, the composition comprises, in parts by weight: 50 parts of tetra- glycidyl amine epoxy resin, 20 parts of phenolic epoxy resin, 15 parts of diglycidyl o- phthalate, 24 parts of methyl hexahydrophthalic anhydride, 16 parts of diethyltoluene di- amine, 2 parts of stabilizer, 11 parts of toughening agent, 1.5 parts of silane coupling agent and 5.5 parts of filler.

[0011] Preferably, the preparation method of the tetra-glycidyl amine epoxy resin comprises the steps of: S1, mixing epoxy chloropropane and a catalyst to obtain mixture 1; S2, adding m-xylylenediamine dropwise in mixture 1, and performing initial reaction after the dropwise addition is completed to obtain mixture 2; S3, controlling temperature, adding alkali A dropwise, and performing second reaction after the dropwise addition is completed to obtain mixture 3; S4, controlling temperature, adding alkali B dropwise, and performing third reaction after the dropwise addition is completed to obtain mixture 4; S5, adding toluene in mixture 4 to adjust the solid content, and then standing to separate the lower brine; controlling temperature, continuing to add alkali C dropwise, and performing fourth reaction after the dropwise addition is completed to obtain mixture 5; S6, adjusting pH of mixture 5 to be acidic or neutral, separating, washing with water, and collecting heavy components after vacuum maintenance to obtain the tetra-glycidyl amine epoxy resin.

[0012] Further preferably, the preparation method of the tetra-glycidyl amine epoxy resin comprises the steps of: S1, mixing 3.5-8 moles of epoxy chloropropane, 0.01-0.1 moles of catalyst at 10-50°C to obtain mixture 1; S2, adding 0.5-2 moles of m-xylylenediamine dropwise in mixture 1, and performing initial reaction for 3-5h after the dropwise addition is completed for 10-25h to obtain mixture 2; S3, controlling temperature to be 25-80°C, adding 0.1-5 moles of alkali A dropwise, and performing second reaction for 20-30min after the dropwise addition is completed for 10-30min to obtain mixture 3; S4, controlling temperature to be 25-80°C, adding 3-10 moles of alkali B dropwise, and performing third reaction for 1-8h after the dropwise addition is completed for 30-90min to obtain mixture 4; S5, adding toluene in mixture 4 to adjust the solid content to be 10%-70%, and then standing for more than 30min to separate the lower brine; controlling temperature to be 25-80°C, continuing to add 0.2-2 moles of alkali C dropwise, and performing fourth reaction for 4-10h after the dropwise addition is completed for 30-60min to obtain mixture 5; S6, the mixture 5 is adjusted to acidic or neutral, separated, washed with water, and after maintaining at 50-70℃ under vacuum, the heavy component is collected at 80-90℃ to obtain the tetraglycidyl amine epoxy resin.

[0013] Further preferably, in step S1, the catalyst is selected from, but not limited to, at least one of tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, benzylammonium chloride, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, triphenyltetradecylphosphonium chloride, tetrabutylphosphonium bromide, triphenyltetradecylphosphonium chloride.

[0014] Further preferably, in step S1, the molar ratio of the epichlorohydrin to the m-xylylenediamine in step S2 is 3.5-8:1; more preferably 4.5-6:1; and more preferably 5:1.

[0015] Further preferably, in step S1, the molar ratio of the epichlorohydrin to the catalyst is 4.5-6:0.01-0.1; more preferably 4.5-6:0.02-0.08; and more preferably 5:0.05.

[0016] Further preferably, in step S1, the mixing is carried out at a temperature of 20-30℃; and more preferably at 25℃.

[0017] Further preferably, in step S2, the dropping is carried out for a time of 18-22h; and more preferably for 20h.

[0018] Further preferably, in step S2, the initial reaction is carried out for a time of 4h.

[0019] Further preferably, in step S2, the initial reaction is carried out at a temperature of 10-50℃; more preferably at 20-30℃; and more preferably at 25℃.

[0020] Further preferably, in step S3, the temperature is controlled at a temperature of 30-50℃; and more preferably at 40℃.

[0021] Further preferably, in step S3, the mass concentration of the lye A is 10%-50%; more preferably 10%-20%; and more preferably 15%.

[0022] Further preferably, in step S3, the molar weight part of the lye A is 0.2-0.3; and more preferably 0.25 molar weight part.

[0023] Further preferably, in step S3, the time for the dropwise addition is 20 min.

[0024] Further preferably, in step S3, the time for the second reaction is 25 min.

[0025] Further preferably, in step S4, the temperature is 30-50℃; more preferably 40℃.

[0026] Further preferably, in step S4, the mass concentration of the alkali B is 30%-50%; more preferably 32%-35%; more preferably 34%.

[0027] Further preferably, in step S4, the molar weight part of the alkali B is 4-6; more preferably 5 molar weight parts.

[0028] Further preferably, in step S4, the time for the dropwise addition is 50-70 min; more preferably 60 min.

[0029] Further preferably, in step S4, the time for the third reaction is 5-6 h.

[0030] Further preferably, in step S5, the solid content is adjusted to 25%-30%.

[0031] Further preferably, in step S5, the time for the standing is 30-90 min; more preferably 30-60 min.

[0032] Further preferably, in step S5, the temperature is 30-50℃; more preferably 40℃.

[0033] Further preferably, in step S5, the mass concentration of the alkali C is 5%-20%; more preferably 10%-15%; more preferably 12%.

[0034] Further preferably, in step S5, the molar weight part of the alkali C is 1-1.5.

[0035] Further preferably, in step S5, the time for the dropwise addition is 40-45 min.

[0036] Further preferably, in step S5, the time for the fourth reaction is 6-8 h; more preferably 7 h.

[0037] Further preferably, in step S6, the pH is adjusted using an acid or acid salt with a mass concentration of 1%-30%; the acid or acid salt is an acid or acid salt commonly used in the art, not limited to hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, sodium dihydrogen phosphate or potassium dihydrogen phosphate; further preferably, the mass concentration is 10%-15%.

[0038] Further preferably, in step S6, the pH is adjusted to 5-7; within the range of pH=5-7, the technical problem of the present application can be solved, not limited to pH=5-6, pH=6-7, pH=5-5.5, pH=5.5-6, pH=6-6.5, pH=6.5-7, pH=5, pH=5.2, pH=5.4, pH=5.6, pH=5.8, pH=6, pH=6.2, pH=6.4, pH=6.6, pH=6.8, pH=7.

[0039] Further preferably, in step S6, the vacuum condition is that the vacuum degree is greater than 0.095 MPa and the temperature is 60±2℃.

[0040] Further preferably, in step S6, the heavy components are collected by the thin film evaporator at a temperature of 85±2℃.

[0041] Further preferably, the alkali A in step S3, the alkali B in step S4 and the alkali C in step S5 are sodium hydroxide.

[0042] Preferably, the stabilizer can be the stabilizer of the existing various one-component type adhesives with epoxy resin as the main agent, from the perspective of improving the storage stability effect, the stabilizer includes but is not limited to at least one of decanedioic acid di(2,2,6,6-tetramethyl-4-piperidyl) ester (CAS 52829-07-9), aluminum chelate, salicylic acid, and tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester.

[0043] Preferably, the toughening agent is selected from at least one of carboxyl-terminated butyl nitrile rubber (CTBN), hydroxyl-terminated butyl nitrile rubber (HTBN), and polyether sulfone (PES).

[0044] Preferably, the silane coupling agent is selected from at least one of γ-aminopropyl triethoxysilane (KH-550), γ-glycidyl ether propyl trimethoxysilane (KH-560), and vinyl trimethoxysilane.

[0045] Preferably, the filler is selected from inorganic fillers; further preferably, the inorganic fillers include but are not limited to aluminum oxide, calcium carbonate, silicon dioxide, titanium dioxide, and zinc oxide.

[0046] Then, the present invention provides a method for preparing the tetraglycidylamine epoxy resin in the above composition, comprising the steps of: ①, epichlorohydrin and a catalyst are mixed to obtain a mixture 1; ②, m-xylenediamine was added dropwise to mixture 1, and an initial reaction was carried out after the addition was completed to obtain mixture 2; ③. Adjust the temperature and add alkali solution A dropwise. After the addition is complete, perform a second reaction to obtain mixture 3. ④. Adjust the temperature and add alkali solution B dropwise. After the addition is complete, perform a third reaction to obtain mixture 4. ⑤. Toluene was added to the mixture 4 to adjust the solid content, and then the mixture was allowed to stand and the lower brine was separated; the temperature was adjusted and the alkali solution C was continued to be added dropwise. After the addition was completed, the fourth reaction was carried out to obtain the mixture 5; ⑥. Adjust the pH of the mixture 5 to acidic or neutral, separate the liquids, wash with water, maintain under vacuum, and collect the heavy components to obtain tetraglycidylamine epoxy resin.

[0047] Preferably, the preparation method of the tetraglycidylamine epoxy resin comprises the steps of: ①, mixing 3.5-8 mol parts by weight of epichlorohydrin and 0.01-0.1 mol parts by weight of a catalyst at 10-50° C. to obtain a mixture 1; ②, 0.5-2 mol weight parts of m-xylenediamine were added dropwise to mixture 1, and after 10-25 hours of addition, an initial reaction was carried out for 3-5 hours to obtain mixture 2; ③. Adjust the temperature to 25-80°C, add 0.1-5 mol parts by weight of alkali solution A dropwise for 10-30 minutes, and then carry out a second reaction for 20-30 minutes to obtain mixture 3; ④. Adjust the temperature to 25-80°C, add 3-10 mol parts by weight of alkali solution B dropwise for 30-90 minutes, and then carry out a third reaction for 1-8 hours to obtain mixture 4; ⑤. Toluene was added to the mixture 4 to adjust the solid content to 10%-70%, and then the mixture was allowed to stand for more than 30 minutes to separate the lower brine; the temperature was adjusted to 25-80°C, and 0.2-2 mol parts by weight of alkali solution C were continuously added dropwise. After the addition was completed over 30-60 minutes, a fourth reaction was carried out for 4-10 hours to obtain a mixture 5; ⑥. Adjust the pH of mixture 5 to acidic or neutral, separate the liquids, wash with water, maintain vacuum at 50-70°C, and collect the heavy components at 80-90°C to obtain tetraglycidylamine epoxy resin.

[0048] Further preferably, in step ①, the catalyst is selected from, but not limited to, at least one of tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, benzylammonium chloride, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, triphenyltetradecylphosphonium chloride, tetrabutylphosphonium bromide, triphenyltetradecylphosphonium chloride.

[0049] Further preferably, the molar ratio of the epichlorohydrin to the m-xylylenediamine in step ① is 3.5-8:1; more preferably 4.5-6:1; more preferably 5:1.

[0050] Further preferably, the molar ratio of the epichlorohydrin to the catalyst in step ① is 4.5-6:0.01-0.1; more preferably 4.5-6:0.02-0.08; more preferably 5:0.05.

[0051] Further preferably, in step ①, the mixing is carried out at a temperature of 20-30℃; more preferably 25℃.

[0052] Further preferably, in step ②, the dropping is carried out for a time of 18-22h; more preferably 20h.

[0053] Further preferably, in step ②, the initial reaction is carried out for a time of 4h.

[0054] Further preferably, in step ②, the initial reaction is carried out at a temperature of 10-50℃; more preferably 20-30℃; more preferably 25℃.

[0055] Further preferably, in step ③, the temperature is controlled at a temperature of 30-50℃; more preferably 40℃.

[0056] Further preferably, in step ③, the mass concentration of the lye A is 10%-50%; more preferably 10%-20%; more preferably 15%.

[0057] Further preferably, in step ③, the molar weight part of the lye A is 0.2-0.3; more preferably 0.25 molar weight part.

[0058] Further preferably, in step ③, the dropping is carried out for a time of 20min.

[0059] Further preferably, in step ③, the second reaction is carried out for a time of 25min.

[0060] Further preferably, in step ④, the temperature is controlled at 30-50℃; more preferably at 40℃.

[0061] Further preferably, in step ④, the mass concentration of the lye B is 30%-50%; more preferably 32%-35%; more preferably 34%.

[0062] Further preferably, in step ④, the molar weight part of the lye B is 4-6; more preferably 5 molar weight parts.

[0063] Further preferably, in step ④, the dropping is performed for 50-70 min; more preferably for 60 min.

[0064] Further preferably, in step ④, the third reaction is performed for 5-6 h.

[0065] Further preferably, in step ⑤, the solid content is adjusted to 25%-30%.

[0066] Further preferably, in step ⑤, the standing is performed for 30-90 min; more preferably for 30-60 min.

[0067] Further preferably, in step ⑤, the temperature is controlled at 30-50℃; more preferably at 40℃.

[0068] Further preferably, in step ⑤, the mass concentration of the lye C is 5%-20%; more preferably 10%-15%; more preferably 12%.

[0069] Further preferably, in step ⑤, the molar weight part of the lye C is 1-1.5.

[0070] Further preferably, in step ⑤, the dropping is performed for 40-45 min.

[0071] Further preferably, in step ⑤, the fourth reaction is performed for 6-8 h; more preferably for 7 h.

[0072] Further preferably, in step ⑥, the pH is adjusted using an acid or an acid salt with a mass concentration of 1%-30%; the acid or the acid salt is an acid or an acid salt commonly used in the art, not limited to hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, sodium dihydrogen phosphate or potassium dihydrogen phosphate; more preferably, the mass concentration is 10%-15%.

[0073] Further preferably, in step ⑥, the pH is adjusted to 5-7; within the range of pH=5-7, the technical problem of the present application can be solved, and it is not limited to pH=5-6, pH=6-7, pH=5-5.5, pH=5.5-6, pH=6-6.5, pH=6.5-7, pH=5, pH=5.2, pH=5.4, pH=5.6, pH=5.8, pH=6, pH=6.2, pH=6.4, pH=6.6, pH=6.8, pH=7.

[0074] Further preferably, in step ⑥, the vacuum condition is that the vacuum degree is greater than 0.095 MPa and the temperature is 60±2℃.

[0075] Further preferably, in step ⑥, the temperature for collecting the heavy components is 85±2℃.

[0076] Further preferably, the alkali A in step ③, the alkali B in step ④, and the alkali C in step ⑤ are sodium hydroxide.

[0077] Further, the present application provides a preparation method of the above composition, comprising the steps of: (1) uniformly mixing tetraglycidyl amine epoxy resin, phenolic resin, and phthalic acid diglycidyl ester to obtain a resin mixture; (2) mixing the resin mixture with methylhexahydrophthalic anhydride, diethyltoluene diamine, silane coupling agent, and filler to obtain a mixture A; (3) mixing and dispersing mixture A with stabilizer and toughening agent to obtain the composition.

[0078] Preferably, in steps (1) and (2), the mixing temperature is 90-110℃; further preferably, the mixing temperature is 100℃.

[0079] Preferably, in steps (1) and (2), the mixing speed is 500-2000r / min; further preferably, in steps (1) and (2), the mixing speed is 500-1000r / min.

[0080] Preferably, in steps (1) and (2), the mixing time is 15-30min; further preferably, in steps (1) and (2), the mixing time is 20min.

[0081] Preferably, in step (3), the mixing temperature is 80-100℃; further preferably, the mixing temperature is 90℃.

[0082] Preferably, in step (3), the dispersing is specifically 1000-3000 r / min, and the dispersing time is 30-60 min; further preferably, in step (3), the dispersing is specifically 2000 r / min, and the dispersing time is 40 min Finally, the application provides the use of the above-mentioned composition in aerospace products, electronic products, automotive manufacturing products, integrated circuit packaging materials.

[0083] Compared with the prior art, the application has the following beneficial effects: 1. The application prepares a tetraglycidyl amine epoxy resin with low viscosity, which is mixed with a phenolic epoxy resin and a diglycidyl phthalate, and interacts with methyl hexahydrophthalic anhydride, diethyl toluene diamine, a toughening agent and other auxiliary agents to form a composition product with excellent mechanical properties, electrical properties and stability.

[0084] 2. In the composition of the application, the proportion of the tetraglycidyl amine epoxy resin is high, and under the condition of a specific fixing agent and a toughening agent, the brittleness of the product is reduced, and the mechanical properties and stability are significantly improved.

[0085] 3. The glycidyl amine type epoxy resin of the application is connected to benzene in the form of an epoxy propyl ether or directly connected to an aliphatic hydrocarbon. In addition, it contains a flexible group (ether bond) and four epoxy groups in the molecule, and reacts with a curing agent to form a crosslinked network structure. Compared with ordinary epoxy resin cured products, it has better mechanical properties, compression and tensile strength, arc resistance and weather resistance, can be used in harsh climates, has good solvent resistance and heat resistance, can be used for bonding of metals and non-metals, manufacturing of solvent-resistant sealant and glass steel, etc. Due to the stable chemical properties, it can also be used for insulating electrical materials, integrated circuit packaging materials, etc., to meet the differentiated needs of the market. DETAILED DESCRIPTION

[0086] The following non-limiting examples can enable those skilled in the art to more fully understand the present application, but do not limit the present application in any way. The following content is only an exemplary description of the scope of the present application, and those skilled in the art can make various changes and modifications to the present application based on the disclosed content, which should also belong to the scope of the present application.

[0087] When the examples give numerical ranges, it should be understood that, unless otherwise specified by the present application, each numerical range has two endpoints and any number between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as generally understood by those skilled in the art to which the present application belongs.

[0088] The application will be further described in the following specific examples. The various chemical reagents used in the examples are obtained by conventional commercial routes unless otherwise specified. In some specific examples, the purchase information of some raw materials is shown in Table 1, and the products from different manufacturers do not have a significant effect on the results.

[0089] Table 1

[0090] Example 1 A method for preparing a tetraglycidyl amine epoxy resin is as follows: ①, 5 mol of epichlorohydrin and 0.05 mol of tetramethylammonium chloride are mixed at 25°C to obtain a mixture 1; ②, 1 mol of m-xylene diamine is added dropwise to the mixture 1, and the dropwise addition is completed in 20 h, and an initial reaction is performed at 25°C for 4 h to obtain a mixture 2; ③, the temperature is controlled at 40°C, 0.25 mol of alkali A (mass concentration 15%) is added dropwise, and after the dropwise addition is completed in 20 min, a second reaction is performed for 25 min to obtain a mixture 3; ④, the temperature is controlled at 40°C, 5 mol of alkali B (mass concentration 34%) is added dropwise, and after the dropwise addition is completed in 60 min, a third reaction is performed for 5 h to obtain a mixture 4; ⑤, toluene is added to the mixture 4 to adjust the solid content to 30%, and then the mixture is left to stand for 60 min, and the lower layer of brine is separated; the temperature is controlled at 40°C, 1 mol of alkali C (mass concentration 12%) is continuously added dropwise, and after the dropwise addition is completed in 40 min, a fourth reaction is performed for 7 h to obtain a mixture 5; ⑥, the pH of the mixture 5 is adjusted to 6, the mixture is separated and washed with water for three times, and then vacuum is maintained at 60±2°C for 1 h, and then the recombined components are collected by a thin film evaporator at 85±2°C to obtain a tetraglycidyl amine epoxy resin.

[0091] Example 2 A method for preparing a tetraglycidyl amine epoxy resin is as follows: ①, 4.5 mol of epichlorohydrin and 0.02 mol of tetramethylammonium bromide are mixed at 20°C to obtain a mixture 1; ②, 1 mol of m-xylene diamine is added dropwise to the mixture 1, and the dropwise addition is completed in 18 h, and an initial reaction is performed at 20°C for 5 h to obtain a mixture 2; ③, the temperature is controlled at 50°C, 0.3 mol of alkali A (mass concentration 20%) is added dropwise, and after the dropwise addition is completed in 30 min, a second reaction is performed for 20 min to obtain a mixture 3; ④, the temperature is controlled at 50°C, 4 mol of alkali B (mass concentration 30%) is added dropwise, and after the dropwise addition is completed in 50 min, a third reaction is performed for 6 h to obtain a mixture 4; ⑤、mixing 4 is added toluene, adjust the solid content to 25%, then stand for 30 min, separate the lower brine; adjust the temperature to 50℃, continue to add 1.5 mol of base liquid C (mass concentration 5%), 45 min after the dropwise addition is completed, carry out the fourth reaction for 8h, to obtain mixture 5; ⑥, mixture 5 is adjusted to pH 5, separated, washed with water three times, vacuum 60±2℃ for 1h, then collect the heavy components at 85±2℃ by thin film evaporator to obtain tetraglycidyl amine epoxy resin.

[0092] Example 3 A method for preparing a tetraglycidyl amine epoxy resin is: ①, 6 mol of epichlorohydrin, 0.08 mol of tetramethylammonium hydroxide are mixed at 30℃ to obtain mixture 1; ②, 1 mol of m-xylene diamine is added dropwise to mixture 1, 28h after the dropwise addition is completed, carry out the initial reaction at 30℃ for 3h to obtain mixture 2; ③, adjust the temperature to 30℃, add 0.2 mol of base liquid A (mass concentration 10%) dropwise, 10 min after the dropwise addition is completed, carry out the second reaction for 30 min to obtain mixture 3; ④, adjust the temperature to 30℃, add 6 mol of base liquid B (mass concentration 50%) dropwise, 70 min after the dropwise addition is completed, carry out the third reaction for 5h to obtain mixture 4; ⑤, add toluene to mixture 4, adjust the solid content to 30%, then stand for 90 min, separate the lower brine; adjust the temperature to 30℃, continue to add 2 mol of base liquid C (mass concentration 20%) dropwise, 40 min after the dropwise addition is completed, carry out the fourth reaction for 6h to obtain mixture 5; ⑥, adjust the pH of mixture 5 to 7, separate, wash with water three times, vacuum 60±2℃ for 1h, then collect the heavy components at 85±2℃ by thin film evaporator to obtain tetraglycidyl amine epoxy resin.

[0093] Comparative Example 1 The difference from Example 1 is that the addition method of base liquid is different.

[0094] A method for preparing a tetraglycidyl amine epoxy resin is: ①, 5 mol of epichlorohydrin, 0.05 mol of tetramethylammonium chloride are mixed at 25℃ to obtain mixture 1; ②, 1 mol of m-xylene diamine is added dropwise to mixture 1, 20h after the dropwise addition is completed, carry out the initial reaction at 25℃ for 4h to obtain mixture 2; ③, adjust the temperature to 40℃, add 6.25 mol of base liquid (mass concentration 15%) dropwise, 120 min after the dropwise addition is completed, carry out the reaction for 7 min to obtain mixture 3; IV. The mixture 3 was added toluene to adjust the solid content to 30%, and then was allowed to stand for 60 min, and the lower layer of brine was separated. The pH was adjusted to 6, and the mixture was separated, washed with water three times, and then was maintained at 60±2°C under vacuum for 1 h. The heavy component was collected by thin film evaporator at 85±2°C to obtain the tetraglycidyl amine epoxy resin.

[0095] Example 4 A composition containing tetraglycidyl amine epoxy resin, the components of which are as follows in parts by weight: 50 parts of tetraglycidyl amine epoxy resin (Example 1), 20 parts of phenolic epoxy resin, 15 parts of diglycidyl o-phthalate, 24 parts of methyl hexahydrophthalic anhydride, 16 parts of diethyl toluene diamine, 2 parts of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, 11 parts of CTBN, 1.5 parts of γ-aminopropyl triethoxysilane, and 5.5 parts of silicon dioxide.

[0096] The preparation method of the composition is as follows: (1) The tetraglycidyl amine epoxy resin, phenolic resin, and diglycidyl o-phthalate were mixed at 100°C and a rotation speed of 1000 r / min for 20 min to obtain a resin mixture; (2) The resin mixture, methyl hexahydrophthalic anhydride, diethyl toluene diamine, γ-aminopropyl triethoxysilane, and silicon dioxide were mixed at 100°C and a rotation speed of 1000 r / min for 20 min to obtain mixture A; (3) Mixture A, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, and CTBN were mixed at 90°C and dispersed at a rotation speed of 2000 r / min for 40 min to obtain the composition.

[0097] Example 5 A composition containing tetraglycidyl amine epoxy resin, the components of which are as follows in parts by weight: 45 parts of tetraglycidyl amine epoxy resin (Example 1), 18 parts of phenolic epoxy resin, 13 parts of diglycidyl o-phthalate, 20 parts of methyl hexahydrophthalic anhydride, 13 parts of diethyl toluene diamine, 1.5 parts of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, 10 parts of CTBN, 1.3 parts of γ-aminopropyl triethoxysilane, and 5 parts of silicon dioxide.

[0098] The preparation method of the composition is the same as that of Example 1.

[0099] Example 6 A composition containing tetra-glycidyl amine epoxy resin, the components are as follows in parts by weight: 55 parts of tetra-glycidyl amine epoxy resin (Example 1), 22 parts of phenolic epoxy resin, 18 parts of diglycidyl phthalate, 26 parts of methyl hexahydrophthalic anhydride, 18 parts of diethyl toluene diamine, 2.5 parts of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 13 parts of CTBN, 2 parts of γ-aminopropyl triethoxysilane and 6 parts of silicon dioxide.

[0100] The preparation method of the composition is the same as Example 1.

[0101] Example 7 A composition containing tetra-glycidyl amine epoxy resin, the components are as follows in parts by weight: 40 parts of tetra-glycidyl amine epoxy resin (Example 2), 15 parts of phenolic epoxy resin, 10 parts of diglycidyl phthalate, 15 parts of methyl hexahydrophthalic anhydride, 10 parts of diethyl toluene diamine, 1 part of salicylic acid, 8 parts of HTBN, 1 part of γ-glycidyl ether oxypropyl trimethoxysilane and 3 parts of aluminum oxide.

[0102] The preparation method of the composition is as follows: (1) The tetra-glycidyl amine epoxy resin, phenolic resin and diglycidyl phthalate are mixed at 90℃ and 2000r / min for 30min to obtain a resin mixture; (2) The resin mixture, methyl hexahydrophthalic anhydride, diethyl toluene diamine, γ-glycidyl ether oxypropyl trimethoxysilane and aluminum oxide are mixed at 90℃ and 2000r / min for 30min to obtain a mixture A; (3) The mixture A and salicylic acid, HTBN are mixed at 100℃, and dispersed at 3000r / min for 30min to obtain the composition.

[0103] Example 8 A composition containing tetra-glycidyl amine epoxy resin, the components are as follows in parts by weight: 60 parts of tetra-glycidyl amine epoxy resin (Example 3), 25 parts of phenolic epoxy resin, 20 parts of diglycidyl phthalate, 30 parts of methyl hexahydrophthalic anhydride, 20 parts of diethyl toluene diamine, 3 parts of di(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 16 parts of PES, 2.2 parts of vinyl trimethoxysilane and 7 parts of calcium carbonate.

[0104] The preparation method of the composition is as follows: (1) The tetra-glycidyl amine epoxy resin, phenolic resin and diglycidyl phthalate are mixed at 110℃ and 5000r / min for 15min to obtain a resin mixture; (2) The resin mixture was mixed with methylhexahydrophthalic anhydride, diethyltoluene diamine, vinyltrimethoxysilane and calcium carbonate at 110°C for 15 minutes at a rotation speed of 5000 r / min to obtain a mixture A; (3) The mixture A and di(2,2,6,6-tetramethyl-4-piperidyl) sebacate, PES were mixed at 80°C, and dispersed at 1000 r / min for 60 minutes to obtain a composition.

[0105] Comparative Example 2 Different from Example 4, the component tetraglycidyl amine epoxy resin was replaced by triglycidyl p-aminophenol (TGPAP). The rest was the same as Example 4.

[0106] Comparative Example 3 Different from Example 4, the component CTBN was replaced by liquid chlorobutyl rubber. The rest was the same as Example 4.

[0107] Comparative Example 4 Different from Example 4, the component methylhexahydrophthalic anhydride was replaced by bis[3-(3-mercaptopropyl)-4-(3-mercaptopropoxy)phenyl]sulfone (C 20 H 28 O4S2). The rest was the same as Example 4.

[0108] Comparative Example 5 Different from Example 4, the component diethyltoluene diamine was replaced by m-phenylenediamine. The rest was the same as Example 4.

[0109] Comparative Example 6 Different from Example 4, the weight ratio of each component in the composition was different. Specifically: A composition containing tetraglycidyl amine epoxy resin, the components were as follows in terms of weight parts: 50 parts of tetraglycidyl amine epoxy resin (Example 1), 5 parts of phenolic epoxy resin, 30 parts of diglycidyl phthalate, 10 parts of methylhexahydrophthalic anhydride, 30 parts of diethyltoluene diamine, 5 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 5 parts of CTBN, 5 parts of γ-aminopropyl triethoxysilane and 5 parts of silicon dioxide. The rest was the same as Example 4.

[0110] Comparative Example 7 Different from Example 4, the tetraglycidyl amine epoxy resin used was the tetraglycidyl amine epoxy resin prepared in Comparative Example 1. The rest was the same as Example 1.

[0111] Test 1 Viscosity detection The viscosity of the tetraglycidyl amine epoxy resin prepared by the preparation method of the application was detected by a rotary viscometer method (GB / T 2794-2013 / ISO 2555). The viscosity results are shown in Table 2.

[0112] Table 2

[0113] As can be seen from Table 2, the tetraglycidyl amine epoxy resin prepared by the preparation method of the application has lower viscosity, significantly improves the wettability and flowability of the substrate, and can significantly improve the mechanical properties of the adhesive as an excellent raw material component.

[0114] Test 2: Mechanical property detection The compositions prepared by Examples 4-8 and Comparative Examples 2-7 were cured at 120℃ for 2h and 160℃ for 2h, and the mechanical properties were detected.

[0115] The test method of impact strength, bending strength and tensile strength was GB / T 2567-2021, and the detection results are shown in Table 3.

[0116] Table 3

[0117] As can be seen from Table 3, in the composition of the application, the interaction of tetraglycidyl amine epoxy resin, phenolic epoxy resin and diglycidyl phthalate improves the adhesion of the composition under the action of specific components, and further improves the mechanical properties; methylhexahydrophthalic anhydride and diethyltoluene diamine as curing agent components, the toughening agent with specific amount and components reacts with the epoxy resin to improve the adhesive properties of the adhesive composition, and further improve the heat distortion temperature and tensile strength of the adhesive. Compared with Comparative Examples 2-5 of conventional components, the impact strength, bending strength and tensile strength of the composition of the application are significantly increased; the components of the application cooperate with each other in a specific ratio to bring excellent mechanical properties of the product, and the mechanical property strength is significantly improved compared with that of Comparative Example 6. Finally, Comparative Example 7 changes the preparation method of the component tetraglycidyl amine epoxy resin, and further changes the adhesion of the main component to form a relatively weak interface layer, and further reduces the mechanical properties such as tensile strength.

[0118] Test 3: Thermal stability detection The thermal stability was detected by TMA method: the resin was mixed uniformly, degassed and poured into a 60mm×15mm×1mm mold, cured at 120℃ for 2h and 160℃ for 2h. Then every 30 minutes was reduced by 10℃-15℃ to room temperature to obtain a test sample. The test was carried out under the condition of 50℃-350℃ range and amplitude 40μm, and the loss tangent tanδ was read. The glass transition temperature value (Tg) was recorded The compositions prepared in Examples 4-8, Comparative Example 2-7, and the Tg results are shown in Table 4.

[0119] Table 4

[0120] As can be seen from Table 4, the composition of the present application has excellent thermal stability under the action of tetraglycidyl amine epoxy resin, phenolic epoxy resin, diglycidyl phthalate and other components, and the technical scheme of the present application significantly improves the Tg value compared with Comparative Example 2-7.

[0121] Finally, it should be noted that the above content is only used to illustrate the technical scheme of the present application, and is not a limitation on the protection scope of the present application. Simple modifications or equivalent replacements of the technical scheme of the present application made by those skilled in the art do not deviate from the essence and scope of the technical scheme of the present application.

Claims

1. A composition containing tetraglycidylamine epoxy resin, characterized in that, The raw materials include, by weight, 40-60 parts of tetraglycidylamine epoxy resin, 15-25 parts of phenolic epoxy resin, 10-20 parts of diglycidyl phthalate, 15-30 parts of methylhexahydrophthalic anhydride, 10-20 parts of diethyltoluenediamine, 1-3 parts of stabilizer, 8-16 parts of toughening agent, 1-2.2 parts of silane coupling agent and 3-7 parts of filler.

2. The composition according to claim 1, characterized in that The raw materials include, by weight, 45-55 parts of tetraglycidylamine epoxy resin, 18-22 parts of phenolic epoxy resin, 13-18 parts of diglycidyl phthalate, 20-26 parts of methylhexahydrophthalic anhydride, 13-18 parts of diethyltoluenediamine, 1.5-2.5 parts of stabilizer, 10-13 parts of toughening agent, 1.3-2 parts of silane coupling agent and 5-6 parts of filler.

3. The composition according to claim 2, characterized in that The raw materials include, by weight, 50 parts of tetraglycidylamine epoxy resin, 20 parts of phenolic epoxy resin, 15 parts of diglycidyl phthalate, 24 parts of methylhexahydrophthalic anhydride, 16 parts of diethyltoluenediamine, 2 parts of stabilizer, 11 parts of toughening agent, 1.5 parts of silane coupling agent and 5.5 parts of filler.

4. The composition according to any one of claims 1 to 3, characterized in that The preparation method of the tetraglycidylamine epoxy resin comprises the steps of: S1, mixing epichlorohydrin and a catalyst to obtain a mixture 1; S2, m-xylenediamine is added dropwise to mixture 1, and an initial reaction is performed after the addition is complete to obtain mixture 2; S3, regulating the temperature, adding alkali solution A dropwise, and performing a second reaction after the addition is complete to obtain mixture 3; S4, regulating the temperature, adding alkali solution B dropwise, and after the addition is complete, performing a third reaction to obtain mixture 4; S5. Add toluene to the mixture 4 to adjust the solid content, then let it stand and separate the lower brine; The temperature was adjusted and the alkali solution C was continued to be added dropwise. After the addition was completed, a fourth reaction was performed to obtain a mixture 5; S6. Adjust the pH of the mixture 5 to acidic or neutral, separate the liquids, wash with water, maintain under vacuum, and collect the heavy components to obtain tetraglycidylamine epoxy resin.

5. The composition according to claim 4, characterized in that The preparation method of the tetraglycidylamine epoxy resin comprises the steps of: S1, mixing 3.5-8 mol parts by weight of epichlorohydrin and 0.01-0.1 mol parts by weight of a catalyst at 10-50° C. to obtain a mixture 1; S2, 0.5-2 mol weight parts of m-xylenediamine are added dropwise to mixture 1, and after 10-25 hours of addition, an initial reaction is carried out for 3-5 hours to obtain mixture 2; S3, regulating the temperature at 25-80° C., adding 0.1-5 mol parts by weight of alkali solution A dropwise, and performing a second reaction for 20-30 min after the addition is completed for 10-30 min to obtain mixture 3; S4, regulating the temperature at 25-80° C., adding 3-10 mol parts by weight of alkali solution B dropwise, and after 30-90 minutes of dropwise addition, performing a third reaction for 1-8 hours to obtain mixture 4; S5. Add toluene to the mixture 4 to adjust the solid content to 10%-70%, then let it stand for more than 30 minutes to separate the lower brine; adjust the temperature to 25-80°C, continue to dropwise add 0.2-2 mol parts by weight of alkali solution C, and after 30-60 minutes of dropwise addition, carry out a fourth reaction for 4-10 hours to obtain a mixture 5; S6. Adjust the pH of the mixture 5 to acidic or neutral, separate the liquids, wash with water, maintain the mixture under vacuum at 50-70° C., and collect the heavy components at 80-90° C. to obtain tetraglycidylamine epoxy resin.

6. The composition according to any one of claims 1 to 3, characterized in that The stabilizer includes but is not limited to at least one of di(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, aluminum chelate, salicylic acid, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; The toughening agent is selected from at least one of carboxyl-terminated nitrile rubber, hydroxyl-terminated nitrile rubber, and polyethersulfone; The silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and vinyltrimethoxysilane; The filler is selected from inorganic fillers.

7. A method for preparing a tetraglycidylamine epoxy resin in a composition according to any one of claims 1 to 6, characterized in that: Including steps: ①, epichlorohydrin and a catalyst are mixed to obtain a mixture 1; ②, m-xylenediamine was added dropwise to mixture 1, and an initial reaction was carried out after the addition was completed to obtain mixture 2; ③. Adjust the temperature and add alkali solution A dropwise. After the addition is complete, perform a second reaction to obtain mixture 3. ④. Adjust the temperature and add alkali solution B dropwise. After the addition is complete, perform a third reaction to obtain mixture 4. ⑤. Add toluene to the mixture 4 to adjust the solid content, then let it stand and separate the lower brine; The temperature was adjusted and the alkali solution C was continued to be added dropwise. After the addition was completed, a fourth reaction was performed to obtain a mixture 5; ⑥. Adjust the pH of the mixture 5 to acidic or neutral, separate the liquids, wash with water, maintain under vacuum, and collect the heavy components to obtain tetraglycidylamine epoxy resin.

8. The method for preparing the composition according to any one of claims 1 to 6, characterized in that: Including steps: (1) uniformly mixing tetraglycidylamine epoxy resin, phenolic resin, and diglycidyl phthalate to obtain a resin mixture; (2) mixing the resin mixture with methylhexahydrophthalic anhydride, diethyltoluenediamine, a silane coupling agent, and a filler to obtain a mixture A; (3) Mixing and dispersing the mixture A, the stabilizer, and the toughening agent to obtain a composition.

9. The preparation method according to claim 8, characterized in that In step (1) and step (2), the mixing temperature is 90-110° C., the mixing speed is 500-2000 r / min, and the mixing time is 15-30 min; In step (3), the mixing temperature is 80-100°C; the dispersion is specifically: 1000-3000 r / min, and the dispersion time is 30-60 min.

10. Use of the composition according to any one of claims 1 to 6 or the composition prepared by the preparation method according to any one of claims 8 to 9 in aerospace products, electronic products, automobile manufacturing products, and integrated circuit packaging materials.

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