A glycidylamine epoxy resin, its preparation method and application

Abstract

This invention relates to the field of epoxy resin technology, specifically to a glycidylamine epoxy resin, its preparation method, and its applications. The glycidylamine epoxy resin provided by this invention has low viscosity and good processability. When used as a modifier in epoxy resins, it increases the length and flexibility of the carbon chains, and the diepoxy groups react with the curing agent to form a cross-linked network, improving the impact strength and tensile strength of the epoxy resin, thereby significantly enhancing its overall mechanical properties. The glycidylamine epoxy resin provided by this invention, when used for epoxy resin modification, can significantly improve the mechanical properties of cured epoxy resins, especially impact resistance and tensile strength. It also reduces viscosity, expanding the application range of epoxy resin materials. The resulting modified epoxy resin can be used in adhesives, coatings, composite materials, electronic components, and microelectronic packaging materials, etc.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin technology, specifically to a glycidylamine epoxy resin, its preparation method, and its application. Background Technology

[0002] Epoxy resin (EP), as one of the most important thermosetting materials today, is widely used in coatings, adhesives, composite materials, and electronic packaging due to its excellent mechanical and adhesive properties. Currently, over 90% of commercially available epoxy resins are bisphenol A glycidyl ether (DGEBA). DGEBA possesses many advantages, including excellent insulation and bonding capabilities. However, like many general-purpose plastics, DGEBA also has some drawbacks, such as high viscosity, difficulty in casting and processing, and excessive rigidity of the three-dimensional network formed by crosslinking after curing, resulting in brittleness and poor toughness, making it difficult to meet the high-performance requirements of cutting-edge fields.

[0003] Existing methods for improving the performance of DGEBA typically involve using DGEBA as the base resin and adding modifiers. Common modifiers include rigid particles, rubber, thermoplastic resins, and core-shell particles. However, currently used modifiers have several drawbacks, such as complex preparation processes, expensive raw materials, and the potential for decreased rigidity, processability, and high-temperature resistance in the final cured product. For example, Chinese patent CN115160515A discloses an amphiphilic liquid crystal block copolymer type epoxy resin toughening agent, which achieves good toughening effects at an addition amount of 5 wt%, but its large molecular weight can easily lead to poor processability of the epoxy resin product. Chinese patent CN109232896A discloses an organosilicon type epoxy resin toughening agent, which can improve impact strength and heat distortion temperature of the cured product, but the long silica chains in the structure of this type of toughening agent may lead to a decrease in the rigidity of the cured product, failing to retain the excellent mechanical properties of epoxy resin. Therefore, there is an urgent need to develop a low-viscosity epoxy resin modifier that can improve multiple mechanical properties such as rigidity and toughness of epoxy resin. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a glycidylamine epoxy resin, its preparation method, and its application. The glycidylamine epoxy resin provided by this invention has low viscosity, good processability, and can significantly improve the rigidity and toughness of epoxy resins simultaneously with low addition amounts.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a glycidylamine epoxy resin having the structure shown in Formula I:

[0007]

[0008] Wherein, R is a saturated alkyl group of C5 to C15.

[0009] This invention provides a method for preparing the glycidylamine epoxy resin described in the above technical solution, comprising the following steps:

[0010] Under the action of a catalyst, m-phenylenediamine undergoes a ring-opening addition reaction with epichlorohydrin to obtain chloroalcoholamine;

[0011] The structural formula of the m-phenylenediamine is as follows:

[0012] The structural formula of the chloroethanolamine is as follows:

[0013] The chloroethanolamine was subjected to a ring-closing reaction with an alkali metal hydroxide to obtain glycidylamine epoxy resin.

[0014] Preferably, the molar ratio of m-phenylenediamine to epichlorohydrin is 1:2 to 8.

[0015] Preferably, the catalyst comprises a phase transfer catalyst and a small molecule polar alcohol.

[0016] Preferably, the phase transfer catalyst comprises a quaternary ammonium salt;

[0017] The total mass ratio of m-phenylenediamine and epichlorohydrin to the mass ratio of the phase transfer catalyst is 100:0.1-2.

[0018] Preferably, the small molecule polar alcohol includes one or more of methanol, ethanol, n-propanol, and isopropanol;

[0019] The molar ratio of the m-phenylenediamine to the small molecule polar alcohol is 1:0.5 to 8.

[0020] Preferably, the ring-opening addition reaction is carried out at a temperature of 20–80°C for 1–8 hours.

[0021] Preferably, the molar ratio of the chloroamine to the alkali metal hydroxide is 1:2 to 4.

[0022] Preferably, the closed-loop reaction is carried out at a temperature of 20–50°C for 2–6 hours.

[0023] This invention provides the application of the glycidylamine epoxy resin described in the above-described technical solution or the glycidylamine epoxy resin prepared by the above-described technical solution in epoxy resin modification.

[0024] The glycidylamine epoxy resin provided by this invention has low viscosity and good processability. When used as a modifier in epoxy resins, it increases the length and flexibility of the carbon chain, and the di-epoxy groups react with the curing agent to form a cross-linked network, improving the impact strength and tensile strength of the epoxy resin, thereby significantly enhancing its overall mechanical properties. The glycidylamine epoxy resin provided by this invention, when used for epoxy resin modification, can significantly improve the mechanical properties of cured epoxy resins, especially their impact resistance and tensile strength. It also reduces viscosity, expanding the application range of epoxy resin materials. The resulting modified epoxy resin can be used in adhesives, coatings, composite materials, electronic components, and microelectronic packaging materials. As shown in the test results of the examples, the impact strength of the modified epoxy resin cured with added glycidylamine epoxy resin can reach 24.59 kJ / m. 2 It has a tensile strength of up to 71.07 MPa, a flexural strength of up to 108.25 MPa, and the viscosity of epoxy resin can be reduced to 6250 cP, exhibiting excellent comprehensive mechanical properties.

[0025] This invention uses epichlorohydrin and m-phenylenediamine as raw materials, and carries out a ring-opening reaction under the action of a catalyst, followed by a ring-closing reaction under alkali metal hydroxide conditions to prepare glycidylamine epoxy resin. This invention employs a two-step method to prepare glycidylamine epoxy resin, which is simple to process, easy to operate, has mild reaction conditions, low raw material costs, low production costs, is environmentally friendly, and suitable for industrial production. Attached Figure Description

[0026] Figure 1 The infrared spectra of the raw material isoheptyl-m-phenylenediamine (IHMXDA) and the prepared glycidylamine epoxy resin (IHMGA) in Example 1 are shown.

[0027] Figure 2 The images show the 1H NMR spectra of the raw material isoheptyl-m-phenylenediamine (IHMXDA) and the prepared glycidylamine epoxy resin (IHMGA) in Example 1. Detailed Implementation

[0028] This invention provides a glycidylamine epoxy resin having the structure shown in Formula I:

[0029]

[0030] In this invention, R is a saturated alkyl group of C5 to C15, and the C5 to C15 group preferably includes C5, C6, C7, C8, C9, C10, C11, C12, C13, C14 or C15. In this invention, R specifically preferably includes isohexyl, isoheptyl, isooctyl or isodecyl.

[0031] This invention provides a method for preparing the glycidylamine epoxy resin described in the above technical solution, comprising the following steps:

[0032] Under the action of a catalyst, m-phenylenediamine undergoes a ring-opening addition reaction with epichlorohydrin to obtain chloroalcoholamine;

[0033] The structural formula of the m-phenylenediamine is as follows:

[0034] The structural formula of the chloroethanolamine is as follows:

[0035] The chloroethanolamine was subjected to a ring-closing reaction with an alkali metal hydroxide to obtain glycidylamine epoxy resin.

[0036] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0037] In this invention, m-phenylenediamine is reacted with epichlorohydrin in the presence of a catalyst to undergo a ring-opening addition reaction to obtain chloroalcoholamine;

[0038] The structural formula of the m-phenylenediamine is as follows:

[0039] The structural formula of the chloroethanolamine is as follows:

[0040] In the m-phenylenediamine and chloroethanolamine, R is the same as R in Formula I.

[0041] In this invention, the molar ratio of the m-phthalamide to epichlorohydrin is preferably 1:2 to 8, more preferably 1:3 to 7, and even more preferably 1:4 to 6. Specifically, it is preferably 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, or 1:8. In this invention, the m-phthalamide preferably includes isohexyl m-phthalamide, isoheptyl m-phthalamide, isooctyl m-phthalamide, or isodecyl m-phthalamide.

[0042] In this invention, the catalyst preferably comprises a phase transfer catalyst and a small molecule polar alcohol.

[0043] In this invention, the phase transfer catalyst preferably comprises a quaternary ammonium salt, which preferably comprises one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride. In this invention, the mass ratio of the total mass of the m-phenylenediamine and epichlorohydrin to the mass of the phase transfer catalyst is preferably 100:0.1–2, more preferably 100:0.5–1.5, further preferably 100:1–1.2, and specifically preferably 100:0.5, 100:0.6, 100:0.7, 100:0.8, 100:0.9, 100:1, 100:1.1, 100:1.2, 100:1.3, 100:1.4, or 100:1.5.

[0044] In this invention, the small molecule polar alcohol preferably includes one or more of methanol, ethanol, n-propanol, and isopropanol. In this invention, the molar ratio of the m-phenylenediamine to the small molecule polar alcohol is preferably 1:0.5 to 8, more preferably 1:1 to 6, further preferably 1:2 to 5, and specifically preferably 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, or 1:8.

[0045] In this invention, the ring-opening addition reaction is preferably carried out under conditions of a co-catalyst or without a co-catalyst. In this invention, the co-catalyst preferably comprises water. In this invention, the molar ratio of the m-phenylenediamine to the co-catalyst is preferably 1:0 to 8, more preferably 1:0, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, or 1:8.

[0046] In this invention, the ring-opening addition reaction of m-phenylenediamine and epichlorohydrin under the action of a catalyst preferably includes: mixing m-phenylenediamine and a catalyst at room temperature, heating to the temperature of the ring-opening addition reaction, and then adding epichlorohydrin dropwise to carry out the ring-opening addition reaction. In this invention, the dropwise addition time of epichlorohydrin is preferably 1-5 hours, more preferably 1-3 hours. This invention does not have a particular limitation on the mixing method; any mixing method well known to those skilled in the art that can ensure uniform mixing of the raw materials is acceptable, such as stirring.

[0047] In this invention, the temperature of the ring-opening addition reaction is preferably 20–80°C, more preferably 30–70°C, and further preferably 40–60°C, specifically preferably 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, or 80°C; the time of the ring-opening addition reaction is preferably 1–8 h, more preferably 2–7 h, and further preferably 3–6 h, specifically preferably 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, or 8 h; the time of the ring-opening addition reaction begins to be counted from the end of the epichlorohydrin addition. This invention does not have a special limitation on the apparatus used for the ring-opening addition reaction; any apparatus well known to those skilled in the art can be used, such as a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and condenser.

[0048] After the ring-opening addition reaction is completed, the present invention cools the ring-opening addition reaction system to the temperature of the ring-closing reaction without the need for gas post-treatment.

[0049] After obtaining chloroethanolamine, the present invention performs a ring-closing reaction between the chloroethanolamine and an alkali metal hydroxide to obtain glycidylamine epoxy resin.

[0050] In this invention, the molar ratio of the chloroamine to the alkali metal hydroxide is preferably 1:2 to 4, more preferably 1:2.5 to 3.5, and specifically preferably 1:2, 1:2.5, 1:3, 1:3.5, or 1:4. In this invention, the alkali metal hydroxide preferably includes one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide, more preferably sodium hydroxide; the alkali metal hydroxide is preferably used in the form of a solid or an aqueous solution, and the concentration of the aqueous solution is preferably 10 to 60 wt%, more preferably 20 to 50 wt%, and even more preferably 30 to 40 wt%. In this invention, the solid alkali metal hydroxide is preferably added in batches. This invention does not have a special limitation on the number of batches of solid alkali metal hydroxide added, as long as it can prevent a rapid temperature rise due to violent exothermic reactions; the aqueous solution of the alkali metal hydroxide is preferably added dropwise. The batch addition of solid alkali metal hydroxide or the dropwise addition of aqueous solution of alkali metal hydroxide in this invention can improve the safety of the reaction.

[0051] In this invention, the temperature of the closed-loop reaction is preferably 20-50°C, more preferably 30-40°C, and specifically preferably 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, or 50°C; the time of the closed-loop reaction is preferably 2-6 hours, more preferably 3-5 hours, and specifically preferably 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours.

[0052] After completing the closed-loop reaction, the present invention preferably further includes post-processing, which preferably includes: solid-liquid separation of the obtained closed-loop reaction system; washing and distilling the obtained liquid components sequentially to obtain a distillate (epimachloropropane) and a residue; and solid-liquid separation of the residue to obtain a liquid component of glycidylamine epoxy resin. The present invention does not have any particular limitation on the solid-liquid separation; any solid-liquid separation method well known to those skilled in the art can be used, such as filtration, vacuum filtration, or centrifugation. In the present invention, the washing solvent preferably includes water or a saturated sodium chloride solution, more preferably a saturated sodium chloride solution. The present invention does not have any particular limitation on the number of washes or the method of washing; any washing method well known to those skilled in the art can be used to wash the organic phase to neutrality, such as using a separatory funnel. The present invention does not have any particular limitation on the distillation; any distillation method well known to those skilled in the art can be used, such as vacuum distillation. The purpose of the distillation is to recover epichloropropane, and the recovered epichloropropane can be recycled.

[0053] This invention provides the application of the glycidylamine epoxy resin described in the above-described technical solutions, or the glycidylamine epoxy resin prepared by the above-described preparation method, in the modification of epoxy resins. In this invention, the glycidylamine epoxy resin is preferably used as a modifier in the modification of epoxy resins, and more preferably in the modification of bisphenol A epoxy resins.

[0054] The present invention also provides a modified epoxy resin, the raw materials of which include epoxy resin, modifier and curing agent; the modifier includes glycidylamine epoxy resin as described in the above technical solution or glycidylamine epoxy resin prepared by the preparation method described in the above technical solution.

[0055] In this invention, the mass ratio of epoxy resin to modifier is preferably 100:1 to 100, more preferably 100:2 to 50, and even more preferably 100:2.5 to 10.

[0056] In this invention, the curing agent preferably includes an amine curing agent, more preferably 4,4-diaminodiphenylmethane (DDM). This invention does not have a specific limitation on the amount of the curing agent used; the theoretical amount is used, determined based on the epoxy value of the epoxy resin and the modifier.

[0057] The present invention also provides a method for preparing the modified epoxy resin described in the above technical solution, comprising the following steps: mixing epoxy resin, modifier and curing agent and then curing to obtain modified epoxy resin.

[0058] The present invention does not have any particular limitation on the mixing method. Any mixing method known to those skilled in the art that can mix the raw materials evenly can be used, such as stirring.

[0059] In this invention, the curing is preferably programmed curing, which preferably includes curing at 95–105°C for 1.5–2.5 hours, curing at 125–135°C for 1.5–2.5 hours, and then curing at 155–165°C for 1.5–2.5 hours; more preferably, curing at 100°C for 2 hours, curing at 130°C for 2 hours, and then curing at 160°C for 2 hours. This invention does not have a particular limitation on the heating rate to each curing temperature; heating rates well known to those skilled in the art can be used.

[0060] After curing, the present invention preferably further includes aging the obtained cured product to obtain a modified epoxy resin. The present invention does not have any particular limitation on the aging process; commonly used aging conditions in the art can be used, such as standing at room temperature for 7 days.

[0061] This invention provides modified epoxy resins as described in the above-described technical solutions or modified epoxy resins prepared by the methods described in the above-described technical solutions. The modified epoxy resins provided by this invention combine excellent rigidity and toughness, expanding the application range of epoxy resin materials. The resulting modified epoxy resins have promising applications in mechanical construction, adhesives, coatings, composite materials, electronic components, and microelectronic packaging materials.

[0062] To further illustrate the present invention, the following detailed description of glycidylamine epoxy resin, its preparation method, and its application are provided in conjunction with embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0063] In the following examples, the secondary m-phenylenediamine used was provided by Anhui Shengao Chemical Technology Co., Ltd., and the other raw materials were provided by Anhui Xinyuan Technology Co., Ltd.

[0064] In the following examples, the epoxy value of the glycidylamine epoxy resin was tested using a potentiometric titrator according to GB / T4612-2008; the viscosity was tested using a DV2T viscometer according to GB / T 22314-2008. In the following application examples, the mechanical properties of the cured epoxy resin were determined using a universal testing machine and an impact testing machine according to GB / T2567-2008.

[0065] Example 1

[0066] Isoheptyl-m-phenylenediamine (IHMXDA), benzyltriethylammonium chloride, water and ethanol were mixed evenly and heated to 40°C. Epichlorohydrin was added dropwise over 1 hour, and the reaction was maintained at this temperature for 1 hour after the addition was complete.

[0067] The mass ratio of isoheptyl-m-phenylenediamine: benzyltriethylammonium chloride: water: ethanol: epichlorohydrin is 332: 2.58: 18: 60: 185.

[0068] The temperature was lowered to 20°C, and solid sodium hydroxide was added in batches. The reaction was carried out for 2 hours, with the mass ratio of isoheptyl-m-phenylenediamine to sodium hydroxide being 332:80. After filtration, the liquid component was washed with saturated sodium chloride solution until neutral. The organic phase was subjected to vacuum distillation to recover excess epichlorohydrin. The residue was filtered again, and the liquid component was isoheptyl-m-phenylenediamine diglycidylamine (IHMGA), with an epoxy value of 0.327 mol / 100 g and a viscosity (25°C) of 627 cP.

[0069] Figure 1 The infrared spectra of isoheptyl-m-phenylenediamine and isoheptyl-m-phenylenediamine diglycidylamine are shown in IHMXDA at 3200–3500 cm⁻¹. -1 The flat and broad peak is the stretching vibration peak of NH, 1217 cm⁻¹. -1 The peak for the stretching vibration of CN is located at 1250 cm⁻¹. However, in IHMGA, the NH stretching vibration peak disappears, and the CN stretching vibration peak redshifts to 1250 cm⁻¹. -1 Peak shape enhancement at 960 cm⁻¹ -1 A new epoxy group absorption peak appeared at the location, indicating that the present invention has successfully prepared glycidylamine epoxy resin.

[0070] Figure 2 The above are the 1H NMR spectra of isoheptyl-m-phenylenediamine and isoheptyl-m-phenylenediamine diglycidylamine. The deuterated reagent used was deuterated chloroform (CDCl3), which is precipitated at δ = 1.33 × 10⁻⁶ in IHMXDA. -6 The sum of δ = 3.75 × 10 -6 The peaks at δ = 2.35 × 10⁻⁶ represent the characteristic proton peaks of the amino group and the benzyl proton peak, respectively. In IHMGA, the characteristic proton peak of the amino group disappears, and the benzyl proton peak shifts, indicating that IHMXDA successfully underwent an epoxidation reaction with ECH. -6 δ = 2.72 × 10 -6 The peak at that location belongs to the hydrogen in the methylene group on the epoxy group. At δ = 2.85 × 10⁻⁶ -6 The peak at that position belongs to the hydrogen atom of the methine group in the epoxy group. At δ = 2.41 × 10⁻⁶ -6 δ = 2.96 × 10 -6 The peak at that position belongs to the hydrogen in the methylene group bonded to the epoxy group. This indicates that the present invention has successfully prepared glycidylamine epoxy resin.

[0071] Example 2

[0072] Mix isooctyl-m-phenylenediamine, tetrabutylammonium bromide, water and methanol evenly, heat to 80°C, add epichlorohydrin dropwise over 2 hours, and keep the mixture at the temperature for 8 hours after the addition is complete; the mass ratio of isooctyl-m-phenylenediamine:tetrabutylammonium bromide:water:methanol:epoxychlorohydrin is 360:5.73:140:250:277.

[0073] The temperature was lowered to 50℃, and 32wt% sodium hydroxide solution was added dropwise. The reaction was carried out for 4 hours, with the mass ratio of isooctyl-m-phenylenediamine to sodium hydroxide solution being 360:500. After filtration, the liquid component was washed with saturated sodium chloride solution until neutral. The organic phase was subjected to vacuum distillation to recover excess epichlorohydrin. The residue was filtered again, and the liquid component was isooctyl-m-phenylenediamine diglycidylamine (IOMGA), with an epoxy value of 0.301 mol / 100g and a viscosity (25℃) of 683 cP.

[0074] Example 3

[0075] Isohexyl-m-phenylenediamine, trioctylmethylammonium chloride and ethanol were mixed evenly and heated to 25°C. Epichlorohydrin was added dropwise over 2 hours. After the addition was complete, the mixture was kept at the temperature for 6 hours. The mass ratio of isohexyl-m-phenylenediamine:trioctylmethylammonium chloride:ethanol:epicochlorohydrin was 304:0.7:25:370.

[0076] The temperature was lowered to 25°C, and solid sodium hydroxide was added in batches. The reaction was carried out for 3 hours, with the mass ratio of isohexylm-phenylenediamine to sodium hydroxide being 304:120. The mixture was filtered, and the liquid component was washed with saturated sodium chloride solution until neutral. The organic phase was subjected to vacuum distillation to recover excess epichlorohydrin. The residue was filtered again, and the liquid component was obtained as isohexylm-phenylenediamine diglycidylamine (IEMGA), with an epoxy value of 0.377 mol / 100 g and a viscosity (25°C) of 601 cP.

[0077] Example 4

[0078] Isodecyl m-phenylenediamine, tetradecyltrimethylammonium chloride and methanol were mixed evenly and heated to 60°C. Epichlorohydrin was added dropwise over 3 hours. After the addition was complete, the mixture was kept at the temperature for 4 hours. The mass ratio of isodecyl m-phenylenediamine: tetradecyltrimethylammonium chloride: methanol: epichlorohydrin was 528:9.28:150:500.

[0079] The temperature was lowered to 35℃, and 32wt% sodium hydroxide solution was added dropwise. The reaction was carried out for 6 hours, with the mass ratio of isodex-m-phenylenediamine to sodium hydroxide solution being 528:394. After filtration, the liquid component was washed with saturated sodium chloride solution until neutral. The organic phase was subjected to vacuum distillation to recover excess epichlorohydrin. The residue was filtered again, and the liquid component was isodex-m-phenylenediamine diglycidylamine (IDMGA), with an epoxy value of 0.288 mol / 100g and a viscosity (25℃) of 712 cP.

[0080] Comparative Application Example 1

[0081] 4,4-Diaminodiphenylmethane (DDM) was added to E-51 epoxy resin and stirred until homogeneous. The mixture was then degassed under vacuum and poured into a mold. The mixture was cured at 100℃ for 2 hours, at 130℃ for 2 hours, and at 160℃ for 2 hours. After curing at room temperature for 7 days, the epoxy resin was aged to obtain the cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin to 4,4-diaminodiphenylmethane was 100:26.42.

[0082] Application Example 1

[0083] The IHMGA prepared in Example 1 was infiltrated into E-51 epoxy resin, and then 4,4-diaminodiphenylmethane was added. The mixture was stirred and mixed evenly, and the air bubbles were removed under vacuum. The mixture was poured into a mold and cured at 100°C for 2 hours, 130°C for 2 hours, and 160°C for 2 hours. After aging at room temperature for 7 days, the modified epoxy resin cured product was obtained. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin to 4,4-diaminodiphenylmethane to IHMGA was 100:26.88:2.5.

[0084] Application Example 2

[0085] The IHMGA prepared in Example 1 was infiltrated into E-51 epoxy resin, and then 4,4-diaminodiphenylmethane was added. The mixture was stirred and mixed evenly, and the air bubbles were removed under vacuum. The mixture was poured into a mold and cured at 100°C for 2 hours, 130°C for 2 hours, and 160°C for 2 hours. After aging at room temperature for 7 days, the modified epoxy resin cured product was obtained. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin to 4,4-diaminodiphenylmethane to IHMGA was 100:27.34:5.

[0086] Application Example 3

[0087] The IHMGA prepared in Example 1 was infiltrated into E-51 epoxy resin, and then 4,4-diaminodiphenylmethane was added. The mixture was stirred and mixed evenly, and the air bubbles were removed under vacuum. The mixture was poured into a mold and cured at 100°C for 2 hours, 130°C for 2 hours, and 160°C for 2 hours. After aging at room temperature for 7 days, the modified epoxy resin cured product was obtained. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin to 4,4-diaminodiphenylmethane to IHMGA was 100:27.8:7.5.

[0088] Application Example 4

[0089] The IHMGA prepared in Example 1 was infiltrated into E-51 epoxy resin, and then 4,4-diaminodiphenylmethane was added. The mixture was stirred and mixed evenly, and the air bubbles were removed under vacuum. The mixture was poured into a mold and cured at 100°C for 2 hours, 130°C for 2 hours, and 160°C for 2 hours. The mixture was then aged at room temperature for 7 days to obtain the modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin to 4,4-diaminodiphenylmethane to IHMGA was 100:28.27:10.

[0090] The mechanical property test results of each epoxy resin cured product are shown in Table 1:

[0091] Table 1. Test results of mechanical properties of epoxy resin cured products

[0092]

[0093] As shown in Table 1, the glycidylamine epoxy resin provided by this invention can significantly improve the impact resistance and toughness of epoxy resin. At a low addition amount (2.5 wt%), the impact strength increases by over 100%, and the elongation at break also increases by nearly 70%. Simultaneously, the rigidity of the epoxy resin is also improved, with tensile strength increasing by nearly 50% and flexural strength slightly increasing. At low addition amounts, the incorporation of the glycidylamine epoxy resin with the structure shown in Formula I provided by this invention greatly enhances the mechanical properties of the cured epoxy resin. The effects of the glycidylamine epoxy resins prepared in Examples 2-4 are similar to those of the IHMGA prepared in Example 1.

[0094] The IHMGA prepared in Example 1 was incorporated into E-51 epoxy resin at amounts of 0, 2.5 wt%, 5 wt%, 7.5 wt%, and 10 wt% of E-51 epoxy resin. The viscosity-reducing properties of the glycidylamine epoxy resin were tested, and the results are shown in Table 2.

[0095] Table 2. Viscosities of E-51 epoxy resin incorporating IHMGA prepared in Example 1

[0096] IHMGA doping amount / wt% 0 2.5 5.0 7.5 10 E-51 epoxy resin viscosity / cP 13680 11300 8750 8633 6250

[0097] As shown in Table 2, the glycidylamine epoxy resin provided by this invention can reduce the viscosity of epoxy resin and improve its processing performance. The effects of the glycidylamine epoxy resins prepared in Examples 2-4 are similar to those of the IHMGA prepared in Example 1.

[0098] In summary, the glycidylamine epoxy resin provided by this invention can significantly improve the mechanical properties and impact resistance of epoxy resin, while also providing a certain viscosity reduction effect. The impact strength of the modified epoxy resin cured product can reach 24.59 kJ / m². 2 It has a tensile strength of up to 71.07 MPa, a flexural strength of up to 108.25 MPa, and the viscosity of epoxy resin can be reduced to 6250 cP, exhibiting excellent comprehensive mechanical properties.

[0099] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. People can obtain other embodiments based on the present invention without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A glycidyl amine epoxy resin having the structure shown in Formula I: ###0001### Formula I wherein R is a saturated alkyl group having 5 to 15 carbon atoms. wherein 2. A method for preparing the glycidyl amine epoxy resin of claim 1, comprising the steps of: carrying out a ring-opening addition reaction of m-xylylenediamine and epichlorohydrin in the presence of a catalyst to obtain a chlorohydrin amine; and carrying out a ring-closing reaction of the chlorohydrin amine with an alkali metal hydroxide to obtain the glycidyl amine epoxy resin. The molar ratio of the m-xylylenediamine to the epichlorohydrin is 1:2 to 8. The catalyst comprises a phase transfer catalyst and a small molecule polar alcohol. The structural formula of the meta-xylylene secondary amine is as follows: The chloralcoholamine has the following structural formula: The phase transfer catalyst comprises a quaternary ammonium salt.

3. The preparation method according to claim 2, characterized in that, The mass ratio of the total mass of the m-xylylenediamine and the epichlorohydrin to the mass of the phase transfer catalyst is 100:0.1 to 2.

4. The production method according to claim 2, characterized by, The small molecule polar alcohol comprises one or more of methanol, ethanol, n-propanol and isopropanol.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the m-xylylenediamine to the small molecule polar alcohol is 1:0.5 to 8. The ring-opening addition reaction is carried out at a temperature of 20 to 80°C for 1 to 8 hours.

6. The preparation method according to claim 4, characterized in that, The molar ratio of the chlorohydrin amine to the alkali metal hydroxide is 1:2 to 4. The ring-closing reaction is carried out at a temperature of 20 to 50°C for 2 to 6 hours.

7. The method of any one of claims 2 to 6, wherein the method further comprises, 10. Use of the glycidyl amine epoxy resin of claim 1 or the glycidyl amine epoxy resin prepared by the method of any one of claims 2 to 9 in the modification of epoxy resins.

8. The preparation method according to claim 2, characterized in that, ​ 9. The production method according to claim 2 or 8, characterized by, ​ ​

Images