Beta-methyl glycidyl ether epoxy compound, preparation method thereof and modified epoxy resin

Abstract

The invention provides a beta-methyl glycidyl ether epoxy compound, a preparation method thereof and modified epoxy resin, and belongs to the technical field of organic synthesis. The beta-methyl glycidyl ether epoxy compound provided by the invention has a structure as shown in a formula I: in the formula I, R is alkyl or polyol group with the carbon atom number of 1-14, and n is 1-4. The methyl epichlorohydrin is used as the raw material, so that the problem of high-value utilization of the industrial byproduct isobutene is solved, and the prepared beta-methyl glycidyl ether epoxy compound is relatively low in viscosity and has the effects of reducing viscosity and toughening. The beta-methyl glycidyl ether epoxy compound provided by the invention is used for epoxy resin modification, the mechanical property and heat resistance of materials such as epoxy resin can be obviously improved, the applicable range of the materials is expanded, and the obtained cured epoxy resin can be used in the fields of electronic printed circuit boards, adhesives or packaging materials and the like. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a beta-methyl glycidyl ether epoxy compound and a preparation method thereof, and a modified epoxy resin. Background Art

[0002] Epoxy resin has excellent bonding properties, mechanical strength, good electrical insulation and chemical stability, and has been widely used in adhesives, electronics and electrical, and automobile manufacturing. However, due to its high viscosity and poor fluidity at room temperature, it is difficult to meet the requirements of construction technology, and diluents need to be added to reduce its viscosity. Common diluents are divided into active diluents and inactive diluents. Active diluents are low-molar mass epoxy compounds containing epoxy groups, such as aliphatic, aromatic, alicyclic glycidyl ethers and their biodegradable compounds. Inactive diluents are inert solvents that do not participate in the curing reaction of epoxy resins, and only achieve physical mixing and reduce viscosity. Inactive diluents will volatilize with the curing reaction, and pores will appear in the resin solid, the shrinkage rate will increase, the adhesion, mechanical strength and heat deformation temperature will decrease, and VOCs emissions will generally be generated.

[0003] Adding epoxy reactive diluents to epoxy resin systems is an important way to improve epoxy resin processes and performance. Methyl epichlorohydrin is an important organic chemical raw material that can be used to synthesize epoxy resins, epoxy reactive diluents, epichlorohydrin rubber, etc. There are two active groups in its molecular structure, epoxy group and chlorine atom, and its chemical properties are very active. Compared with the commonly used epichlorohydrin, methyl epichlorohydrin has a higher boiling point, less volatile loss during use, less skin irritation to workers, and less air pollution. It is an ideal environmentally friendly chemical synthesis raw material. At the same time, methyl epichlorohydrin is an industrial product of isobutylene with abundant output. How to use methyl epichlorohydrin to convert it into high value-added chemical products has become a practical problem that needs to be solved urgently in the industry. Summary of the invention

[0004] The object of the present invention is to provide a β-methyl glycidyl ether epoxy compound and a preparation method thereof, and a modified epoxy resin. The present invention uses methyl epichlorohydrin instead of epichlorohydrin as a raw material to synthesize the β-methyl glycidyl ether epoxy compound, thereby solving the problem of high-value utilization of industrial by-product isobutylene.

[0005] In order to achieve the purpose of the present invention, the present invention provides the following technical solutions:

[0006] A β-methyl glycidyl ether epoxy compound having a structure shown in Formula I:

[0007]

[0008] In formula I, R is a hydrocarbon group or a polyol group having 1 to 14 carbon atoms, and n is 1 to 4.

[0009] Preferably, the R is one of n-butyl, isobutyl, hexyl, propenyl and 1,4-butanediol.

[0010] Preferably, the β-methyl glycidyl ether epoxy compound is one of n-butyl-β-methyl glycidyl ether, isobutyl-β-methyl glycidyl ether, hexyl-β-methyl glycidyl ether, propenyl-β-methyl glycidyl ether and 1,4-butanediol di(β-methyl) glycidyl ether.

[0011] The present invention also provides a method for preparing the β-methyl glycidyl ether epoxy compound described in the above technical solution, comprising the following steps:

[0012] An alcohol having a structure of R-OH, an acidic catalyst and methyl epichlorohydrin are subjected to a ring-opening addition reaction to obtain a chlorohydrin ether having a structure shown in formula II;

[0013] In formula II, R is as defined in formula I;

[0014] The chlorohydrin ether, a phase transfer catalyst and an inorganic base are subjected to a ring-closing reaction to obtain the beta-methyl glycidyl ether epoxy compound.

[0015] Preferably, the acidic catalyst is a Lewis acid;

[0016] The phase transfer catalyst is a quaternary ammonium salt.

[0017] Preferably, the molar ratio of the alcohol to methyl epichlorohydrin is 0.1 to 10:1; the ratio of the mass of the acidic catalyst to the sum of the mass of the alcohol and methyl epichlorohydrin is 0.01 to 10:100;

[0018] The ratio of the mass of the phase transfer catalyst to the sum of the mass of the alcohol, the inorganic base and methyl epichlorohydrin is 0.01 to 10:100;

[0019] The molar ratio of the chlorohydrin ether to the inorganic base is preferably 1:1-10.

[0020] Preferably, the ring-opening reaction is carried out at a temperature of 20 to 100° C. and for a time of 1 to 12 h;

[0021] The temperature of the ring-closing reaction is 20 to 80° C., and the time is 2 to 12 hours.

[0022] The present invention also provides a modified epoxy resin, which is a modified epoxy resin using the β-methyl glycidyl ether epoxy compound described in the above technical solution or the β-methyl glycidyl ether epoxy compound prepared by the preparation method described in the above technical solution as a modifier.

[0023] Preferably, the following components are included:

[0024] Epoxy resin;

[0025] A β-methyl glycidyl ether epoxy compound accounting for 1 to 20% by mass of the epoxy resin;

[0026] A curing agent that matches the epoxy value of the epoxy resin.

[0027] The present invention provides a β-methyl glycidyl ether epoxy compound having a structure shown in Formula I: in Formula I, R is a hydrocarbon group or a polyol group having 1 to 14 carbon atoms, and n is 1 to 4. The present invention uses methyl epichlorohydrin instead of traditional epichlorohydrin as a raw material to synthesize a new structure β-methyl glycidyl ether epoxy compound, which not only solves the problem of excess industrial byproduct isobutylene, but also the prepared β-methyl glycidyl ether epoxy compound has a low viscosity and has the effects of reducing viscosity and increasing toughness. In addition, the preparation method of the β-methyl glycidyl ether epoxy compound of the present invention is simple to operate and has broad market application prospects.

[0028]

[0029] The present invention also provides a modified epoxy resin, which is prepared by mixing the β-methyl glycidyl ether epoxy compound described in the above technical solution or the β-methyl glycidyl ether epoxy compound prepared by the preparation method described in the above technical solution, epoxy resin and curing agent, and then curing and aging in sequence. The β-methyl glycidyl ether epoxy compound provided by the present invention is used for epoxy resin modification, wherein the β-methyl glycidyl ether epoxy compound is cured with the curing agent to form an interpenetrating and semi-interpenetrating network structure with a toughening effect in the epoxy resin network, which can significantly improve the mechanical properties of the epoxy resin, have a viscosity-reducing effect on the epoxy resin, and improve the heat resistance of the epoxy resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. 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 creative labor.

[0031] Figure 1 This is the infrared spectrum of butyl-β-methyl glycidyl ether prepared in Example 1 of the present invention;

[0032] Figure 2 The viscosity diagram of E-51 epoxy resin blended with different amounts of butyl-β-methyl glycidyl ether;

[0033] Figure 3 This is the DSC graph of E-51 epoxy resin and E-51 epoxy resin blended with 7.5wt% butyl-β-methyl glycidyl ether. DETAILED DESCRIPTION

[0034] The present invention provides a β-methyl glycidyl ether epoxy compound having a structure shown in Formula I:

[0035]

[0036] In formula I, R is a hydrocarbon group or a polyol group having 1 to 14 carbon atoms, and n is 1 to 4.

[0037] In the present invention, the R is one of n-butyl, isobutyl, hexyl, propenyl and 1,4-butanediol.

[0038] In the present invention, the β-methyl glycidyl ether epoxy compound is the aliphatic β-methyl glycidyl ether which is one of n-butyl-β-methyl glycidyl ether, isobutyl-β-methyl glycidyl ether, hexyl-β-methyl glycidyl ether, propenyl-β-methyl glycidyl ether and 1,4-butanediol di(β-methyl) glycidyl ether.

[0039] The present invention also provides a method for preparing the β-methyl glycidyl ether epoxy compound described in the above technical solution, comprising the following steps:

[0040] An alcohol having a structure of R-OH, an acidic catalyst and methyl epichlorohydrin are subjected to a ring-opening addition reaction to obtain a chlorohydrin ether having a structure shown in formula II;

[0041] In formula II, R is as defined in formula I;

[0042] The chlorohydrin ether, a phase transfer catalyst and an inorganic base are subjected to a ring-closing reaction to obtain the beta-methyl glycidyl ether epoxy compound.

[0043] In the present invention, unless otherwise specified, all preparation raw materials are commercially available products well known to those skilled in the art or are prepared by preparation methods well known to those skilled in the art.

[0044] The invention carries out a ring-opening addition reaction on an alcohol with a structure of R-OH, an acidic catalyst and methyl epichlorohydrin to obtain a chlorohydrin ether with a structure shown in formula II.

[0045] In the present invention, the alcohol with the structure of R-OH can be an alcohol with 1 to 14 carbon atoms. In a specific embodiment, the alcohol can be a fatty alcohol with 1 to 14 carbon atoms or a polyol with 1 to 14 carbon atoms. In a specific embodiment, the fatty alcohol with 1 to 14 carbon atoms can be methanol, butanol, decanol, undecanol, dodecanol, tridecanol or tetradecanol. In a specific embodiment, the polyol with 1 to 14 carbon atoms can be ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane or pentaerythritol.

[0046] In the present invention, the acidic catalyst may be a Lewis acid; in a specific embodiment, the Lewis acid may be boron trifluoride etherate, TiCl4, InCl3, SnCl4 or a solid acid catalyst supported by the Lewis acid.

[0047] In the present invention, the molar ratio of the alcohol to methyl epichlorohydrin can be 0.1 to 10:1, and in specific embodiments, can be 0.5:1, 1:1, 2:1, 5:1, 6:1 or 8:1; the ratio of the mass of the acidic catalyst to the sum of the mass of the alcohol and methyl epichlorohydrin can be 0.01 to 10:100, and in specific embodiments, can be 0.1:100, 0.4:100, 0.5:100, 0.7:100 or 0.9:100.

[0048] In the present invention, alcohol and an acidic catalyst are first placed in a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer at room temperature for mixing to obtain a mixed system; then the temperature is raised to a temperature required for a ring-opening reaction, methyl epichlorohydrin is mixed with the mixed system to carry out a ring-opening reaction.

[0049] In the present invention, the mixing method of the methyl epichlorohydrin can be dropwise addition. The present invention has no special limitation on the dropwise addition rate of the methyl epichlorohydrin, as long as the temperature does not rise sharply. In the present invention, the reaction temperature of the ring-opening reaction can be 20 to 100°C, and in a specific embodiment, it can be 30°C, 50°C, 70°C or 80°C. In the present invention, the time of the ring-opening reaction starts from the end of the mixing of the methyl epichlorohydrin; the reaction time of the ring-opening reaction can be 1 to 12 hours, and in a specific embodiment, it can be 2 hours, 5 hours, 8 hours or 10 hours.

[0050] After obtaining the chlorohydrin ether, the present invention mixes the chlorohydrin ether, a phase transfer catalyst and an inorganic base to carry out a ring-closing reaction to obtain the beta-methyl glycidyl ether epoxy compound.

[0051] In the present invention, the phase transfer catalyst may be a quaternary ammonium salt; in a specific embodiment, the quaternary ammonium salt may be benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, dodecyldimethyl dipolyglycerol ether ammonium chloride, tetradecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride;

[0052] In the present invention, the inorganic base may be an alkali metal hydroxide; the alkali metal hydroxide may be sodium hydroxide or potassium hydroxide; the sodium hydroxide may be solid sodium hydroxide or a sodium hydroxide solution; the concentration of the sodium hydroxide solution may be 18 to 48 wt%, and in a specific embodiment, may be 28 wt%, 32 wt% or 40 wt%.

[0053] In the present invention, the ratio of the mass of the phase transfer catalyst to the sum of the masses of the alcohol, the inorganic base and methyl epichlorohydrin can be 0.01 to 10:100, and in specific embodiments, can be 0.05:100, 0.1:100, 0.4:100, 0.7:100 or 0.9:100; the molar ratio of the chlorohydrin ether to the inorganic base can be 1:1 to 10, and in specific embodiments, can be 1:3, 1:5, 1:6 or 1:8.

[0054] In the present invention, after the ring-opening reaction is completed, the obtained reaction solution is cooled directly to the temperature required for the ring-closing reaction without post-treatment, and then an inorganic base and a phase transfer catalyst are added to carry out the ring-closing reaction.

[0055] In the present invention, the temperature of the ring-closing reaction can be 20-80°C, and in a specific embodiment, can be 30°C, 50°C or 60°C; the time can be 2-12h, and in a specific embodiment, can be 4h, 6h, 8h or 10h.

[0056] In the present invention, after the ring-closing reaction is completed, post-treatment is also carried out; the post-treatment includes filtering, washing and distilling in sequence; the present invention has no special requirements for the filtration, and the filtration operation commonly used in the field can be adopted; the reagent used for the washing can be water, and the water can be deionized water; the distillation can be reduced pressure distillation.

[0057] In the ring-closing reaction, the present invention provides an alkaline environment by using an inorganic base to remove chlorine atoms from the chlorohydrin ether and close the ring to generate an epoxy group.

[0058] The present invention also provides a modified epoxy resin, which is a modified epoxy resin using the β-methyl glycidyl ether epoxy compound described in the above technical solution or the β-methyl glycidyl ether epoxy compound prepared by the preparation method described in the above technical solution as a modifier.

[0059] In the present invention, the modified epoxy resin comprises the following components:

[0060] Epoxy resin;

[0061] A β-methyl glycidyl ether epoxy compound accounting for 1 to 20% by mass of the epoxy resin;

[0062] A curing agent that matches the epoxy value of the epoxy resin.

[0063] In the present invention, the epoxy resin may be bisphenol A epoxy resin; in a specific embodiment, the bisphenol A epoxy resin may be E-51 epoxy resin.

[0064] In the present invention, the curing agent may be diethylenetriamine.

[0065] In the present invention, the mass ratio of the β-methyl glycidyl ether epoxy compound to the epoxy resin is determined according to the purpose of the epoxy resin cured product; the β-methyl glycidyl ether epoxy compound can be 1 to 20% of the mass of the epoxy resin, and in specific embodiments, it can be 7.5%, 10%, 12.5%, 15% or 18%.

[0066] In the present invention, the quality of the curing agent is determined according to the epoxy value of the epoxy resin; in a specific embodiment, the amount of the curing agent is determined by referring to the book "Curing Agent" published by Chemical Industry Press. Taking diethylenetriamine as the curing agent as an example, the amount calculation formula is as follows:

[0067]

[0068] In the formula: G is the number of grams of curing agent required to cure 100g of epoxy resin, g; M is the relative molecular mass of the curing agent, g / mol; E is the epoxy value of the epoxy resin, mol / 100g; Hn is the total number of active hydrogens in the curing agent molecule.

[0069] In the present invention, the mixing method of the β-methyl glycidyl ether epoxy compound, epoxy resin and curing agent can be stirring. The present invention has no special requirements for the stirring, and the raw materials can be mixed evenly; the curing time and temperature are determined according to the curing kinetics of the resin and the curing agent; the present invention has no special requirements for the aging, and the aging operation commonly used in the art can be adopted.

[0070] In order to further illustrate the present invention, a β-methyl glycidyl ether epoxy compound and its preparation method and modified epoxy resin provided by the present invention are described in detail below in conjunction with the accompanying drawings and examples, but they should not be construed as limiting the scope of protection of the present invention.

[0071] The n-butanol and n-hexanol used in the following examples and comparative examples of the present invention are both of reagent grade and purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; epichlorohydrin is of industrial grade and purchased from Shandong Binhua Group Co., Ltd.; and sodium hydroxide is of industrial grade and purchased from Anhui Xinyuan Technology Co., Ltd.

[0072] Example 1

[0073] 222.4 g of n-butanol and 1.7 g of boron trifluoride etherate were added to a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 60° C. 106.5 g of methyl epichlorohydrin was added dropwise within 1 hour. After the addition was completed, the mixture was kept warm at 60° C. for 5 hours and then cooled to 40° C. 137.5 g of 32 wt% sodium hydroxide solution was added dropwise within 2 hours. After the addition was completed, the mixture was kept warm at 40° C. for 6 hours. The obtained reaction liquid was filtered and washed in turn, and the excess n-butanol was distilled under reduced pressure and recovered to obtain 108.8 g of butyl-β-methyl glycidyl ether, with an epoxy value of 0.4223 mol / 100 g and a viscosity of 2 mPa·s.

[0074] Figure 1 The infrared spectrum of butyl-β-methyl glycidyl ether prepared in Example 1 of the present invention is shown in FIG. Figure 1 The results show that 1114cm -1 COC asymmetric stretching vibration peak, 907 cm -1 is the characteristic peak of the epoxy group, which indicates that the present invention successfully prepared butyl-β-methyl glycidyl ether.

[0075] Example 2

[0076] 148.2 g of n-butanol and 2.6 g of InCl3 were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 60°C. 106.5 g of methyl epichlorohydrin was added dropwise within 1 hour. After the addition was completed, the mixture was kept warm at 60°C for 5 hours. The temperature was lowered to 40°C, 137.5 g of 32 wt% sodium hydroxide solution was added dropwise within 2 hours. After the addition was completed, the mixture was kept warm at 40°C for 6 hours. The obtained reaction liquid was filtered and washed in turn, and the excess n-butanol was distilled under reduced pressure and recovered to obtain 101.8 g of butyl-β-methyl glycidyl ether with an epoxide value of 0.4092 mol / 100 g and a viscosity of 3 mPa·s.

[0077] Example 3

[0078] 245.2 g of n-hexanol and 1.6 g of SnCl4 were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 60°C. 63.9 g of methyl epichlorohydrin was added dropwise within 1 hour. After the addition was completed, the mixture was kept warm at 60°C for 5 hours. The temperature was lowered to 40°C, and 82.5 g of 32 wt% sodium hydroxide solution was added dropwise within 2 hours. After the addition was completed, the mixture was kept warm at 40°C for 6 hours. The obtained reaction liquid was filtered and washed, and the excess n-hexanol was distilled under reduced pressure and recovered to obtain 77.9 g of hexyl-β-methyl glycidyl ether with an epoxide value of 0.3314 mol / 100 g and a viscosity of 5 mPa·s.

[0079] Example 4

[0080] 138.9 g of n-hexanol and 2.2 g of SnCl4 were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 70°C. 63.9 g of methyl epichlorohydrin was added dropwise within 1 hour. After the addition was completed, the mixture was kept warm at 70°C for 5 hours. The temperature was lowered to 40°C, and 82.5 g of 32 wt% sodium hydroxide solution was added dropwise within 2 hours. After the addition was completed, the mixture was kept warm at 40°C for 6 hours. The obtained reaction liquid was filtered and washed, and the excess n-hexanol was distilled under reduced pressure and recovered to obtain 73.8 g of hexyl-β-methyl glycidyl ether with an epoxide value of 0.3677 mol / 100 g and a viscosity of 4 mPa·s.

[0081] Example 5

[0082] 290.4 g of allyl alcohol and 2.4 g of SnCl4 were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, and the temperature was raised to 60° C., 106.6 g of methyl epichlorohydrin was added dropwise within 1 hour, and the mixture was kept warm at 60° C. for 5 hours. The temperature was lowered to 35° C., 125 g of 32 wt% sodium hydroxide solution was added dropwise within 2 hours, and the mixture was reacted for 6 hours. The obtained reaction liquid was filtered and washed, and the excess allyl alcohol was distilled under reduced pressure and recovered to obtain 130 g of allyl-β-methyl glycidyl ether, with an epoxide value of 0.4994 mol / 100 g and a viscosity of less than 2 mPa·s.

[0083] Example 6

[0084] 90 g of 1,4-butanediol and 2.3 g of boron trifluoride etherate were added into a four-necked flask equipped with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, the temperature was raised to 80° C., 370 g of methyl epichlorohydrin was added dropwise within 1 hour, the mixture was kept warm at 80° C. for 5 hours, the temperature was lowered to 35° C., 275 g of 32 wt% sodium hydroxide solution was added dropwise within 2 hours, and the mixture was reacted for 8 hours; the obtained reaction liquid was filtered and washed, and the excess methyl epichlorohydrin was distilled under reduced pressure and recovered to obtain 240 g of 1,4-butanediol di(β-methyl) glycidyl ether, with an epoxy value of 0.4236 mol / 100 g and a viscosity of 20 mPa·s.

[0085] Application Example 1

[0086] 2 g of butyl-β-methyl glycidyl ether prepared in Example 1 was added to 40 g of E-51 epoxy resin, and 4.5 g of diethylenetriamine was added. After stirring evenly, the mixture was cured at room temperature for 12 h, then cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0087] Application Example 2

[0088] 3 g of butyl-β-methyl glycidyl ether prepared in Example 1 was added to 40 g of E-51 epoxy resin, and 4.7 g of diethylenetriamine was added. After stirring evenly, the mixture was cured at room temperature for 12 h, then cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0089] Application Example 3

[0090] 4 g of butyl-β-methyl glycidyl ether prepared in Example 1 was added to 40 g of E-51 epoxy resin, and 4.8 g of diethylenetriamine was added. After stirring evenly, the mixture was cured at room temperature for 12 h, then cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0091] Application Example 4

[0092] 5 g of butyl-β-methyl glycidyl ether prepared in Example 1 was added to 40 g of E-51 epoxy resin, and 4.9 g of diethylenetriamine was added. After stirring evenly, the mixture was cured at room temperature for 12 h, cured at 80°C for 3 h, and aged at room temperature for 7 days to obtain a cured epoxy resin.

[0093] Comparative Example 1

[0094] Take 50g of E-51 epoxy resin, add 5.5g of diethylenetriamine, stir evenly, cure at room temperature for 12h, cure at 80°C for 3h, and age at room temperature for 7 days to obtain a cured epoxy resin.

[0095] Test Case

[0096] The mechanical properties of the epoxy resin cured products prepared in Examples 1 to 4 and Comparative Example 1 were tested, and the results are shown in Table 1.

[0097] Table 1 Mechanical properties of epoxy resin cured products prepared in Application Examples 1 to 4 of the present invention and Comparative Example 1

[0098]

[0099] According to the results in Table 1, with the continuous increase of the addition amount of β-methyl glycidyl ether, the epoxy resin cured product has obvious improvements in bending resistance and impact resistance. When the addition amount is 7.5%, the elongation at break of butyl-β-methyl glycidyl ether / E-51 cured strip is 56.39% higher than that of pure DGEBA, and the impact strength is 17.14KJ / m 2 , which is 56.28% higher than that of pure E-51 cured specimens. In addition, the tensile strength and flexural strength of the cured product are also slightly improved.

[0100] Figure 2 The line graph of viscosity change of E-51 epoxy resin blended with different amounts of butyl-β-methyl glycidyl ether is shown in Figure 1. Figure 2 It can be seen that with the addition of butyl-β-methyl glycidyl ether, the viscosity of the blended epoxy resin system is greatly reduced, which proves that the butyl-β-methyl glycidyl ether prepared by the present invention can play an effect of reducing the viscosity of the epoxy resin.

[0101] Figure 3 The DSC graph of E-51 epoxy resin and E-51 epoxy resin blended with 7.5wt% butyl-β-methyl glycidyl ether is shown in Figure 1. Figure 3 It can be seen that the glass transition temperature of the epoxy resin cured by E-51 with the addition of butyl-β-methyl glycidyl ether is significantly higher than that of the epoxy resin cured by pure E-51, indicating that the addition of butyl-β-methyl glycidyl ether can improve the heat resistance of the epoxy resin.

[0102] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A β-methyl glycidyl ether epoxy compound, characterized in that: It has the structure shown in formula I: In formula I, R is a hydrocarbon group or a polyol group having 1 to 14 carbon atoms, and n is 1 to 4.

2. The β-methyl glycidyl ether epoxy compound according to claim 1, characterized in that: The R is one of n-butyl, isobutyl, hexyl, propenyl and 1,4-butanediol.

3. The β-methyl glycidyl ether epoxy compound according to claim 1, characterized in that: The β-methyl glycidyl ether epoxy compound is one of n-butyl-β-methyl glycidyl ether, isobutyl-β-methyl glycidyl ether, hexyl-β-methyl glycidyl ether, propenyl-β-methyl glycidyl ether and 1,4-butanediol di(β-methyl) glycidyl ether.

4. The method for preparing the β-methyl glycidyl ether epoxy compound according to any one of claims 1 to 3, characterized in that: The following steps are involved: An alcohol having a structure of R-OH, an acidic catalyst and methyl epichlorohydrin are subjected to a ring-opening addition reaction to obtain a chlorohydrin ether having a structure shown in formula II; In formula II, R is as defined in formula I; The chlorohydrin ether, a phase transfer catalyst and an inorganic base are subjected to a ring-closing reaction to obtain the beta-methyl glycidyl ether epoxy compound.

5. The preparation method according to claim 4, characterized in that: The acidic catalyst is a Lewis acid; The phase transfer catalyst is a quaternary ammonium salt.

6. The preparation method according to claim 4, characterized in that: The molar ratio of the alcohol to methyl epichlorohydrin is 0.1 to 10:1; the ratio of the mass of the acidic catalyst to the sum of the mass of the alcohol and methyl epichlorohydrin is 0.01 to 10:100; The ratio of the mass of the phase transfer catalyst to the sum of the mass of the alcohol, the inorganic base and methyl epichlorohydrin is 0.01 to 10:100; The molar ratio of the chlorohydrin ether to the inorganic base is preferably 1:1-10.

7. The preparation method according to claim 4 or 6, characterized in that: The ring-opening reaction is carried out at a temperature of 20 to 100° C. and for a time of 1 to 12 hours; The temperature of the ring-closing reaction is 20 to 80° C., and the time is 2 to 12 hours.

8. A modified epoxy resin, characterized in that A modified epoxy resin using the β-methyl glycidyl ether epoxy compound described in claims 1 to 3 or the β-methyl glycidyl ether epoxy compound prepared by the preparation method described in any one of claims 4 to 7 as a modifier.

9. The modified epoxy resin according to claim 8, characterized in that: Includes the following components: Epoxy resin; A β-methyl glycidyl ether epoxy compound accounting for 1 to 20% by mass of the epoxy resin; A curing agent that matches the epoxy value of the epoxy resin.

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