Epoxy reactive diluent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an epoxy reactive diluent as well as a preparation method and application thereof. The invention provides an epoxy reactive diluent. The structural formula of the epoxy reactive diluent is shown as a formula I, the preparation method of the epoxy reactive diluent comprises the following steps: under the action of a ring-opening catalyst, carrying out ring-opening addition reaction on phenyl alcohol ether and epoxy chloropropane, and then under the action of a ring-closing catalyst, mixing with alkali metal hydroxide to carry out ring-closing reaction, thereby obtaining the epoxy reactive diluent product. The preparation raw materials are low in price, the preparation process is simple, the reaction conditions are mild, the method is green and environment-friendly, and the industrial feasibility is high. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to an epoxy active diluent and a preparation method and application thereof. Background Art

[0002] Epoxy resin (EP), 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 bonding properties. Currently, more than 90% of commercial epoxy resins are bisphenol A glycidyl ether, but they have some shortcomings, such as high viscosity, difficulty in casting, and excessive rigidity of the three-dimensional network produced by cross-linking after curing, resulting in defects such as brittleness and poor toughness, making it difficult to meet the high-performance requirements of cutting-edge fields. To address the problems of high viscosity and difficult casting, epoxy reactive diluents are generally added. Epoxy reactive diluents can directly participate in the curing reaction of epoxy resins, becoming part of the cross-linked network structure of the epoxy resin cured product, thereby modifying the epoxy resin.

[0003] Benzyl glycidyl ether (XY-692) is a common aromatic epoxy reactive diluent with the structural formula shown below:

[0004]

[0005] However, the modified epoxy resin prepared by using benzyl glycidyl ether (XY-692) as an epoxy reactive diluent still has the problems of poor toughness and low impact strength. Summary of the Invention

[0006] In view of this, the object of the present invention is to provide an epoxy reactive diluent and its preparation method and application. The modified epoxy resin prepared using the epoxy reactive diluent of the present invention has high impact strength and tensile strength.

[0007] The present invention provides an epoxy reactive diluent, the structural formula of which is shown in Formula I:

[0008]

[0009] In formula I, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time.

[0010] The present invention also provides a method for preparing the epoxy reactive diluent described in the above technical solution, comprising the following steps:

[0011] In the presence of a ring-opening catalyst, a phenyl alcohol ether and epichlorohydrin are subjected to a ring-opening addition reaction to obtain a chlorohydrin ether; the phenyl alcohol ether is ethylene glycol phenyl ether or propylene glycol phenyl ether;

[0012] The structural formula of the chlorohydrin ether is shown in Formula II:

[0013]

[0014] In formula II, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time;

[0015] Under the action of a ring-closing catalyst, the chlorohydrin ether and the alkali metal hydroxide are mixed to undergo a ring-closing reaction to obtain an epoxy active diluent.

[0016] Preferably, the molar ratio of the phenyl alcohol ether to epichlorohydrin is 1:1-2.

[0017] Preferably, the ring-opening catalyst is a Lewis acid catalyst, and the Lewis acid catalyst includes a Lewis acid homogeneous catalyst or a solid acid catalyst; the Lewis acid homogeneous catalyst includes one or more of a boron trifluoride complex, anhydrous tin tetrachloride, p-toluenesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, zinc trifluoromethanesulfonate, aluminum chloride and zinc perchlorate; the solid acid catalyst includes one or more of a strongly acidic ion exchange resin, strongly acidic ion exchange resin-supported tin tetrachloride, activated carbon-supported boron trifluoride, activated carbon-supported sulfuric acid, montmorillonite-supported aluminum chloride and molecular sieve-supported zinc perchlorate.

[0018] Preferably, the mass ratio of the total mass of the phenyl alcohol ether and epichlorohydrin to the Lewis acid catalyst is 100:0.1-1; when the Lewis acid catalyst is a solid acid catalyst, the weight is calculated based on the acid loading.

[0019] Preferably, the temperature of the ring-opening addition reaction is 30-80° C., and the time is 1-8 hours.

[0020] Preferably, the ring-closing catalyst comprises a phase transfer catalyst, and the phase transfer catalyst comprises one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.

[0021] Preferably, the molar ratio of the chlorohydrin ether to the alkali metal hydroxide is 1:1-2; the temperature of the ring-closure reaction is 20-60°C, and the time is 1-8 hours; and the mass ratio of the chlorohydrin ether to the phase transfer catalyst is 100:0.1-2.

[0022] The present invention also provides the use of the epoxy reactive diluent described in the above technical solution in epoxy resin modification.

[0023] The present invention also provides a modified epoxy resin, the preparation raw materials of which include epoxy resin, diluent and curing agent; the diluent includes the epoxy reactive diluent described in the above technical solution.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention provides an epoxy reactive diluent, the structural formula of which is shown in Formula I. The epoxy reactive diluent of the present invention contains a large number of flexible ether bonds, which can improve the impact strength and tensile strength of modified epoxy resins. The data in the examples show that the impact strength of the modified epoxy resin cured product prepared by adding the epoxy reactive diluent of the present invention can reach 17.18 kJ / m 2 , the tensile strength can reach 69.47MPa, the elongation at break can reach 6.42%, and the impact strength and tensile strength are high.

[0026] The epoxy reactive diluent of the present invention exhibits excellent viscosity reduction effects and can effectively improve the processability of epoxy resin systems when added. Data from the examples show that the viscosity of the epoxy resin system can be reduced to 2317 mPa·s after the addition of the epoxy reactive diluent, demonstrating excellent processability. Modified epoxy resins prepared using the epoxy reactive diluent of the present invention achieve viscosity reduction and basic mechanical properties comparable to or superior to those of benzyl glycidyl ether reactive diluents. The epoxy reactive diluent of the present invention can completely replace benzyl glycidyl ether epoxy reactive diluents.

[0027] The present invention also provides a method for preparing the epoxy reactive diluent described in the above technical solution. The raw materials for the preparation include phenyl alcohol ether and epichlorohydrin, resulting in low raw material costs and unaffected by price fluctuations of benzyl alcohol (the main raw material for benzyl glycidyl ether is benzyl alcohol). The epoxy reactive diluent preparation process of the present invention is simple, easy to operate, has mild reaction conditions, is environmentally friendly, and has high industrial feasibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0029] Figure 1 This is the infrared spectrum of the raw material ethylene glycol phenyl ether and the prepared glycidyl ether epoxy reactive diluent XY-692-a in Example 1. DETAILED DESCRIPTION

[0030] The present invention provides an epoxy reactive diluent, the structural formula of which is shown in Formula I:

[0031]

[0032] In formula I, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time.

[0033] The present invention also provides a method for preparing the epoxy reactive diluent described in the above technical solution, comprising the following steps:

[0034] In the presence of a ring-opening catalyst, a phenyl alcohol ether and epichlorohydrin are subjected to a ring-opening addition reaction to obtain a chlorohydrin ether; the phenyl alcohol ether is ethylene glycol phenyl ether or propylene glycol phenyl ether;

[0035] The structural formula of the chlorohydrin ether is shown in II:

[0036]

[0037] In formula II, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time;

[0038] Under the action of a ring-closing catalyst, the chlorohydrin ether and the alkali metal hydroxide are mixed to undergo a ring-closing reaction to obtain an epoxy active diluent.

[0039] In the present invention, unless otherwise specified, the materials and equipment used are commercially available products in the art.

[0040] The invention conducts a ring-opening addition reaction on phenyl alcohol ether and epichlorohydrin under the action of a ring-opening catalyst to obtain chlorohydrin ether; the phenyl alcohol ether is ethylene glycol phenyl ether or propylene glycol phenyl ether.

[0041] In the present invention, the structural formula of ethylene glycol phenyl ether or propylene glycol phenyl ether is shown in Formula III:

[0042]

[0043] In formula III, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time.

[0044] In the present invention, the molar ratio of the phenyl alcohol ether to epichlorohydrin is preferably 1:1 to 2, more preferably 1:1 to 1.3, specifically 1:1, 1:1.1, 1:1.2 or 1:1.3.

[0045] In the present invention, the ring-opening catalyst is preferably a Lewis acid catalyst, and the Lewis acid catalyst preferably includes a Lewis acid homogeneous catalyst or a solid acid catalyst; the Lewis acid homogeneous catalyst preferably includes one or more of a boron trifluoride complex, anhydrous tin tetrachloride, p-toluenesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, zinc trifluoromethanesulfonate, aluminum chloride and zinc perchlorate; the solid acid catalyst preferably includes one or more of a strongly acidic ion exchange resin, strongly acidic ion exchange resin-loaded tin tetrachloride, activated carbon-loaded boron trifluoride, activated carbon-loaded sulfuric acid, montmorillonite-loaded aluminum chloride and molecular sieve-loaded zinc perchlorate, and the solid acid catalyst is provided by Anhui Xinyuan Technology Co., Ltd.

[0046] In the present invention, the mass ratio of the total mass of the phenyl alcohol ether and epichlorohydrin to the Lewis acid catalyst is preferably 100:0.1 to 1, more preferably 100:0.2 to 0.8, specifically 100:0.2, 100:0.3, 100:0.4, 100:0.5, 100:0.6, 100:0.7 or 100:0.8. The solid acid catalyst is calculated based on the effective ingredient, and the effective ingredient is the loaded amount of the acid.

[0047] In the present invention, the ring-opening addition reaction of epichlorohydrin and phenyl alcohol ether under the action of a ring-opening catalyst preferably includes: mixing the phenyl alcohol ether with the ring-opening catalyst at room temperature, heating to the temperature of the ring-opening addition reaction, and then dripping epichlorohydrin to carry out the ring-opening addition reaction. The dripping time of the epichlorohydrin is preferably 1 to 5 hours, more preferably 2 to 4 hours, specifically 2 hours, 2.5 hours, 3 hours or 4 hours. The purpose of controlling the dripping time in the present invention is to prevent the reaction from being too violent and improve the safety of the reaction. The present invention has no special requirements for the mixing method of the phenyl alcohol ether and the ring-opening catalyst. It is sufficient to use a mixing method well known to those skilled in the art to mix the raw materials evenly, such as stirring and mixing.

[0048] In the present invention, the temperature of the ring-opening addition reaction is preferably 30 to 80°C, more preferably 40 to 70°C, specifically 40°C, 45°C, 50°C, 55°C, 60°C, 65°C or 70°C; the time is preferably 1 to 8 hours, more preferably 2 to 5 hours, specifically 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours; the time of the ring-opening addition reaction is counted from the end of the dropwise addition of epichlorohydrin. The present invention has no special requirements for the apparatus used in the ring-opening addition reaction, and an apparatus well known to those skilled in the art can be used, such as a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser.

[0049] After completing the ring-opening addition reaction, when adopting lewis acid homogeneous catalyst, the ring-opening addition reaction system is cooled to the temperature of the ring-closed reaction by the present invention, without the need to carry out other aftertreatment; When adopting solid acid type catalyst, after the ring-opening addition reaction system is cooled to the temperature of the ring-closed reaction by the present invention, carry out solid-liquid separation process, solid component is solid acid type catalyst, is recycled, and liquid component is chlorohydrin ether, enters follow-up ring-closed reaction.The present invention is not particularly limited for the solid-liquid separation, adopts solid-liquid separation mode well known to those skilled in the art, specifically as filtering, suction filtration or centrifugation.

[0050] After obtaining the chlorohydrin ether, the present invention mixes the chlorohydrin ether and an alkali metal hydroxide in the presence of a ring-closing catalyst to carry out a ring-closing reaction to obtain an epoxy active diluent.

[0051] In the present invention, the ring-closing catalyst preferably includes a phase transfer catalyst, and the phase transfer catalyst preferably includes one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.

[0052] In the present invention, the mass ratio of the chlorohydrin ether to the phase transfer catalyst is preferably 100:0.1-2, more preferably 100:0.5-1.5, specifically 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.

[0053] In the present invention, the molar ratio of the chlorohydrin ether to the alkali metal hydroxide is preferably 1:1-2, more preferably 1:1-1.4, specifically preferably 1:1.1, 1:1.2, 1:1.3 or 1:1.4.

[0054] In the present 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 alkali metal hydroxide solid or alkali metal hydroxide aqueous solution, and the concentration of the alkali metal hydroxide aqueous solution is preferably 10-60wt.%, more preferably 20-50wt.%, further preferably 30-50wt.%, specifically 32wt.% or 48wt.%. The alkali metal hydroxide solid is preferably added in batches. The present invention has no special requirements for the number of batches of the alkali metal hydroxide solid, as long as it can prevent the temperature from rising sharply due to intense heat release; the alkali metal hydroxide aqueous solution is preferably added dropwise, and the dropwise addition time of the alkali metal hydroxide aqueous solution is preferably 1-5h, more preferably 2-4h, specifically 2h, 3h or 4h. The purpose of controlling the dropwise addition time in the present invention is to prevent the reaction from being too violent and improve the safety of the reaction. The present invention adds alkali metal hydroxide solid or drops alkali metal hydroxide aqueous solution in batches, which can improve the safety of the reaction.

[0055] In the present invention, the temperature of the ring-closure reaction is preferably 20 to 60° C., more preferably 30 to 50° C., specifically 30° C., 35° C., 40° C., 45° C., or 50° C.; the time of the ring-closure reaction is preferably 1 to 8 hours, more preferably 2 to 5 hours, specifically 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours. The time of the ring-closure reaction is counted from the completion of the dropwise addition of the alkali metal hydroxide aqueous solution or the completion of the addition of all the alkali metal hydroxide solids.

[0056] After the ring-closure reaction is completed, the present invention preferably further includes a post-treatment, which preferably includes: sequentially salifying and stratifying the resulting ring-closure reaction system; desalting the lower layer material; and sequentially washing and distilling the upper layer material to obtain a distillate and a residual liquid, respectively. The obtained distillate is epichlorohydrin, and the obtained residual liquid is an epoxy reactive diluent. The present invention has no special requirements for salification, and can be carried out in a manner well known to those skilled in the art, such as dissolving in water. The present invention has no special requirements for stratification, and can be carried out in a manner well known to those skilled in the art, such as standing for stratification. The present invention has no special limitations on the desalination treatment, and can be carried out in a manner well known to those skilled in the art. The washing solvent preferably includes water, more preferably tap water. The present invention has no special requirements for the number and method of washing, and can be carried out by washing the organic phase to neutrality using a washing method well known to those skilled in the art, such as washing using a separatory funnel. The present invention has no special requirements for the distillation, and a distillation method well known to those skilled in the art can be used, specifically a combination of atmospheric distillation and reduced pressure distillation. The purpose of the distillation is to recover low-boiling substances such as epichlorohydrin and water, and the recovered epichlorohydrin can be recycled.

[0057] The present invention also provides the use of the epoxy reactive diluent described in the above technical solution or the epoxy reactive diluent prepared by the preparation method described in the above technical solution in epoxy resin modification.

[0058] In the present invention, the epoxy reactive diluent is preferably used as a diluent in epoxy resin modification, more preferably in bisphenol A epoxy resin modification, and the epoxy resin is preferably E-51 epoxy resin.

[0059] The present invention also provides a modified epoxy resin, the preparation raw materials of which include epoxy resin, diluent and curing agent; the diluent includes the epoxy reactive diluent described in the above technical solution or the epoxy reactive diluent prepared by the preparation method described in the above technical solution.

[0060] In the present invention, the mass ratio of the epoxy resin to the diluent is preferably 100:1 to 30, more preferably 100:5 to 15, specifically 100:5, 100:10 or 100:15.

[0061] In the present invention, the curing agent preferably includes an amine curing agent, more preferably diethylenetriamine and butyl glycidyl ether adduct (593) or diethylenetriamine (DETA). The present invention has no particular limitation on the amount of the curing agent used, and the amount is close to the theoretical amount and can be determined based on the epoxy value of the epoxy resin and the diluent.

[0062] The present invention also provides a method for preparing the modified epoxy resin described in the above technical solution, comprising the following steps: mixing the epoxy resin, a diluent and a curing agent and then curing the mixture to obtain the modified epoxy resin.

[0063] The present invention has no special requirements for the mixing method of the epoxy resin, diluent and curing agent. The raw materials can be evenly mixed using a mixing method well known to those skilled in the art, such as stirring.

[0064] In the present invention, the curing is preferably programmed curing, which preferably includes curing at 20-30°C for 10-15 hours, followed by curing at 70-100°C for 2-4 hours. More preferably, the programmed curing comprises curing at 25°C for 12 hours, followed by curing at 80°C for 3 hours. The present invention has no particular requirements for the heating rate to each curing temperature, and a heating rate familiar to those skilled in the art can be used.

[0065] After the curing is completed, the present invention preferably further comprises aging the obtained cured product to obtain a modified epoxy resin. The present invention has no special requirements for the aging, and the aging conditions commonly used in the art can be used, specifically, standing at room temperature for 7 days.

[0066] To further illustrate the present invention, the epoxy reactive diluent provided by the present invention, its preparation method and application are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0067] In the following examples, the epoxy value of the glycidyl ether reactive diluent was measured using a potentiometric titrator according to GB / T4612-2008; the viscosity was measured using a DV2T viscometer according to GB / T 22314-2008. The mechanical properties of the cured epoxy resins in the following application examples were measured using a universal testing machine and an impact testing machine according to GB / T2567-2008.

[0068] Example 1

[0069] Ethylene glycol phenyl ether (EGE) and zinc perchlorate were mixed evenly, heated to 40°C, and epichlorohydrin was added dropwise within 2 hours. After the addition was complete, the mixture was kept warm for 2 hours. The mass ratio of ethylene glycol phenyl ether: zinc perchlorate: epichlorohydrin was 139:1.00:110.

[0070] The temperature was lowered to 30° C., benzyltriethylammonium chloride was added, and the mixture was mixed uniformly. A 32 wt.% aqueous sodium hydroxide solution (hereinafter referred to as liquid caustic soda) was added dropwise over 2 h. After the addition was complete, the mixture was kept warm for 2 h; wherein the mass ratio of sodium hydroxide: benzyltriethylammonium chloride: ethylene glycol phenyl ether was 44:1.38:139; hydrated salt was added, the mixture was allowed to stand for stratification, the upper organic phase was washed with tap water until neutral, and the organic phase was subjected to reduced pressure distillation to recover excess epichlorohydrin, water and other low-boiling substances. The residual liquid was a glycidyl ether epoxy reactive diluent (denoted as XY-692-a) having an epoxy value of 0.37 mol / 100 g, a viscosity (25° C.) of 25 mPa·s, a moisture content of 0.05%, an inorganic chlorine content of 15 mg / kg, an easily saponifiable chlorine content of 2800 ppm, and a chromaticity of 28Pt-Co.

[0071] Figure 1 This is the infrared spectrum of ethylene glycol phenyl ether (EGE) and the prepared glycidyl ether epoxy reactive diluent (XY-692-a). The wavelengths of EGE are 3100-3600 cm -1 The blunt and broad peak at 860 cm is the stretching vibration peak of OH, while in XY-692-a, the OH stretching vibration peak disappears. -1 A new epoxy group absorption peak appeared at , indicating that the glycidyl ether epoxy reactive diluent was successfully prepared.

[0072] Example 2

[0073] Mix ethylene glycol phenyl ether and activated carbon-supported sulfuric acid evenly, heat to 50°C, add epichlorohydrin dropwise over 3 hours, and keep warm for 3 hours after the addition is complete; the mass ratio of ethylene glycol phenyl ether: sulfuric acid: epichlorohydrin is 139:0.68:95;

[0074] The temperature was lowered to 35°C, and activated carbon-supported sulfuric acid was filtered and recovered. Tetrabutylammonium bromide was added and mixed uniformly. 48 wt.% of liquid caustic soda was added dropwise over 2 h. After the addition was complete, the mixture was kept warm for 3 h. The mass ratio of sodium hydroxide: tetrabutylammonium bromide: ethylene glycol phenyl ether was 48:2.58:139. Salt was dissolved, and the mixture was allowed to stand for stratification. The upper organic phase was washed with tap water until neutral. The organic phase was subjected to reduced pressure distillation to recover excess epichlorohydrin, water, and other low-boiling substances. The residual liquid was a glycidyl ether epoxy reactive diluent (denoted as XY-692-b) with an epoxy value of 0.41 mol / 100 g, a viscosity (25°C) of 28 mPa·s, a moisture content of 0.06%, an inorganic chlorine content of 17 mg / kg, a readily saponifiable chlorine content of 2670 ppm, and a color of 28Pt-Co.

[0075] Example 3

[0076] Mix propylene glycol phenyl ether and trifluoromethanesulfonic acid evenly, heat to 60°C, add epichlorohydrin dropwise over 2.5 hours, and keep warm for 4 hours after the addition is complete; the mass ratio of propylene glycol phenyl ether: trifluoromethanesulfonic acid: epichlorohydrin is 153:1.64:120;

[0077] The temperature was lowered to 40°C, dodecyltrimethylammonium chloride was added, and the mixture was mixed uniformly. Solid sodium hydroxide was added in batches within 3 hours, and the mixture was kept warm for 4 hours after the addition was completed; wherein the mass ratio of sodium hydroxide: dodecyltrimethylammonium chloride: propylene glycol phenyl ether was 52:3.71:153; salt was dissolved, and the mixture was allowed to stand for stratification. The upper organic phase was washed with tap water until neutral, and the organic phase was subjected to reduced pressure distillation to recover excess epichlorohydrin, water and other low-boiling substances. The residual liquid was a glycidyl ether epoxy reactive diluent (denoted as XY-692-c) with an epoxy value of 0.29 mol / 100 g, a viscosity (25°C) of 32 mPa·s, a moisture content of 0.08%, an inorganic chlorine content of 16 mg / kg, a readily saponifiable chlorine content of 2500 ppm, and a color of 28Pt-Co.

[0078] Example 4

[0079] Mix propylene glycol phenyl ether and montmorillonite-supported aluminum chloride evenly, heat to 70°C, add epichlorohydrin dropwise over 4 hours, and keep warm for 5 hours after the addition is complete; the mass ratio of propylene glycol phenyl ether: aluminum chloride: epichlorohydrin is 153:2.20:106;

[0080] The temperature was lowered to 50° C., and after filtering and recovering the montmorillonite-loaded aluminum chloride, tetradecyltrimethylammonium chloride was added and mixed uniformly. 32 wt.% of liquid caustic soda was added dropwise over 4 h, and the mixture was kept warm for 5 h after the addition was complete; wherein the mass ratio of sodium hydroxide:tetradecyltrimethylammonium chloride:propylene glycol phenyl ether was 56:2.45:153; salt was dissolved, and the mixture was allowed to stand for stratification. The upper organic phase was washed with tap water until neutral, and the organic phase was subjected to reduced pressure distillation to recover excess epichlorohydrin, water, and other low-boiling substances. The residual liquid was a glycidyl ether epoxy reactive diluent (denoted as XY-692-d) with an epoxy value of 0.23 mol / 100 g, a viscosity (25° C.) of 45 mPa·s, a moisture content of 0.06%, an inorganic chlorine content of 15 mg / kg, a readily saponifiable chlorine content of 2435 ppm, and a color of 28Pt-Co.

[0081] Comparative Application Example 1

[0082] Diethylenetriamine and butyl glycidyl ether adduct (593) were added to E-51 epoxy resin, mixed uniformly, and de-bubbled in vacuo. The mixture was then poured into a mold and cured at 25°C for 12 h, then at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin to 593 was 100:31.

[0083] Comparative Application Example 2

[0084] Commercially available benzyl glycidyl ether reactive diluent (denoted as XY-692-0) was incorporated into E-51 epoxy resin, followed by the addition of 593. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin: 593: XY-692-0 was 100:32:5.

[0085] Comparative Application Example 3

[0086] XY-692-0 was added to E-51 epoxy resin, followed by 593. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin: 593: XY-692-0 was 100:33:10.

[0087] Comparative Application Example 4

[0088] XY-692-0 was added to E-51 epoxy resin, followed by 593. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin: 593: XY-692-0 was 100:34:15.

[0089] Comparative Application Example 5

[0090] Diethylenetriamine (DETA) was added to E-51 epoxy resin, mixed thoroughly, and vacuum-degassing was performed. The mixture was then poured into a mold and cured at 25°C for 12 hours and at 80°C for 3 hours. The mixture was then aged at room temperature for 7 days to obtain a cured epoxy resin. The properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin to DETA was 100:11.

[0091] Comparative Application Example 6

[0092] XY-692-0 was incorporated into E-51 epoxy resin, followed by DETA. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The impact properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin:DETA:XY-692-0 was 100:12:5.

[0093] Comparative Application Example 7

[0094] XY-692-0 was incorporated into E-51 epoxy resin, followed by DETA. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The impact properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin:DETA:XY-692-0 was 100:12:10.

[0095] Comparative Application Example 8

[0096] XY-692-0 was incorporated into E-51 epoxy resin, followed by DETA. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The impact properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin:DETA:XY-692-0 was 100:12:15.

[0097] Application Example 1

[0098] The XY-692-a prepared in Example 1 was incorporated into E-51 epoxy resin, followed by the addition of 593. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and then aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin: 593: XY-692-a was 100:32:5.

[0099] Application Example 2

[0100] The XY-692-a prepared in Example 1 was incorporated into E-51 epoxy resin, and then 593 was added. The mixture was thoroughly mixed, air bubbles were removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and then aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin: 593: XY-692-a was 100:33:10.

[0101] Application Example 3

[0102] The XY-692-a prepared in Example 1 was incorporated into E-51 epoxy resin, and then 593 was added. The mixture was thoroughly mixed, air bubbles were removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and then aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The properties of the cured product are shown in Table 1. The mass ratio of E-51 epoxy resin: 593: XY-692-a was 100:34:15.

[0103] Application Example 4

[0104] The XY-692-a prepared in Example 1 was incorporated into E-51 epoxy resin, followed by diethylenetriamine (DETA). The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The impact properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin:DETA:XY-692-a was 100:12:5.

[0105] Application Example 5

[0106] The XY-692-a prepared in Example 1 was incorporated into E-51 epoxy resin, and DETA was then added. The mixture was thoroughly mixed, air bubbles removed under vacuum, and the mixture was poured into a mold. The mixture was cured at 25°C for 12 hours, then at 80°C for 3 hours, and then aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The impact properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin:DETA:XY-692-a was 100:12:10.

[0107] Application Example 6

[0108] The XY-692-a prepared in Example 1 was incorporated into E-51 epoxy resin, and DETA was then added. The mixture was thoroughly mixed, and air bubbles were removed under vacuum. The mixture was poured into a mold and cured at 25°C for 12 hours, then at 80°C for 3 hours, and then aged at room temperature for 7 days to obtain a modified epoxy resin cured product. The impact properties of the cured product are shown in Table 2. The mass ratio of E-51 epoxy resin:DETA:XY-692-a was 100:12:15.

[0109] The mechanical properties test results of each epoxy resin cured product are shown in Table 1 and Table 2:

[0110] Table 1593 Mechanical properties test results of cured epoxy resin

[0111]

[0112]

[0113] Table 2 Impact resistance test results of DETA cured epoxy resin

[0114]

[0115] As shown in Tables 1 and 2, the glycidyl ether reactive diluent provided by the present invention significantly improves the impact resistance and toughness of epoxy resins, increasing impact strength by up to 40.13% and elongation at break by nearly 45.91% compared to E-51 epoxy resin. Compared to the commercially available XY-692-0 with a similar structure, it exhibits similar modification effects and exhibits superior performance at lower addition levels.

[0116] The XY-692-a prepared in Example 1 was added to E-51 epoxy resin in amounts of 0, 5 wt.%, 10 wt.%, and 15 wt.% of the E-51 epoxy resin, respectively. The viscosity reduction performance of the glycidyl ether reactive diluent was tested, and the results are shown in Table 3.

[0117] Table 3 Viscosity of E-51 epoxy resin mixed with XY-692-a prepared in Example 1

[0118]

[0119] As shown in Table 3, the glycidyl ether reactive diluent provided by the present invention can reduce the viscosity of epoxy resin and improve the processing performance of epoxy resin.

[0120] In summary, the glycidyl ether reactive diluent provided by the present invention can significantly improve the mechanical properties and impact resistance of epoxy resin, and at the same time can provide excellent viscosity reduction effect. Among them, the impact strength of the modified epoxy resin cured product can reach 17.18 kJ / m 2 , the tensile strength can reach 69.47MPa, the elongation at break can reach 6.42%, and the viscosity of the epoxy resin can be reduced to 2317mPa·s, with good comprehensive mechanical properties.

[0121] Although the above embodiments provide a detailed description of the present invention, they are only part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on the embodiments of the present invention without creative work, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. An epoxy reactive diluent, characterized in that The structural formula is shown in Formula I: In formula I, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time.

2. The method for preparing the epoxy reactive diluent according to claim 1, wherein The following steps are involved: In the presence of a ring-opening catalyst, a phenyl alcohol ether and epichlorohydrin are subjected to a ring-opening addition reaction to obtain a chlorohydrin ether; the phenyl alcohol ether is ethylene glycol phenyl ether or propylene glycol phenyl ether; The structural formula of the chlorohydrin ether is shown in Formula II: In formula II, R1 is hydrogen or methyl, R2 is hydrogen or methyl, and R1 and R2 are not methyl at the same time; Under the action of a ring-closing catalyst, the chlorohydrin ether and the alkali metal hydroxide are mixed to undergo a ring-closing reaction to obtain an epoxy active diluent.

3. The preparation method according to claim 2, characterized in that The molar ratio of the phenyl alcohol ether to epichlorohydrin is 1:1-2.

4. The preparation method according to claim 2 or 3, characterized in that The ring-opening catalyst is a Lewis acid catalyst, which includes a Lewis acid homogeneous catalyst or a solid acid catalyst; the Lewis acid homogeneous catalyst includes one or more of a boron trifluoride complex, anhydrous tin tetrachloride, p-toluenesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, zinc trifluoromethanesulfonate, aluminum trichloride and zinc perchlorate; the solid acid catalyst includes one or more of a strongly acidic ion exchange resin, strongly acidic ion exchange resin-supported tin tetrachloride, activated carbon-supported boron trifluoride, activated carbon-supported sulfuric acid, montmorillonite-supported aluminum trichloride and molecular sieve-supported zinc perchlorate.

5. The preparation method according to claim 4, characterized in that The mass ratio of the total mass of the phenyl alcohol ether and epichlorohydrin to the Lewis acid catalyst is 100:0.1-1; when the Lewis acid catalyst is a solid acid catalyst, it is calculated based on the acid loading.

6. The preparation method according to claim 2, characterized in that The temperature of the ring-opening addition reaction is 30-80° C., and the time is 1-8 hours.

7. The preparation method according to claim 2, characterized in that The ring-closing catalyst comprises a phase transfer catalyst, and the phase transfer catalyst comprises one or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.

8. The preparation method according to claim 7, characterized in that The molar ratio of the chlorohydrin ether to the alkali metal hydroxide is 1:1-2; the temperature of the ring-closure reaction is 20-60°C, and the time is 1-8 hours; the mass ratio of the chlorohydrin ether to the phase transfer catalyst is 100:0.1-2.

9. Use of the epoxy reactive diluent according to claim 1 in epoxy resin modification.

10. A modified epoxy resin, characterized in that: The preparation raw materials include epoxy resin, diluent and curing agent; the diluent includes the epoxy reactive diluent according to claim 1.

Images