Phenoxy resin flexibilizer, preparation thereof and application of phenoxy resin flexibilizer in curing and toughening of bisphenol diglycidyl ether compound

Abstract

The invention relates to the field of polymer modification preparation, in particular to a preparation method of a phenoxy resin toughening agent, which comprises the following steps: carrying out epoxy group ring-opening reaction on a bisphenol diglycidyl ether compound and a polyacid compound under the action of triethylamine to obtain the phenoxy resin toughening agent, the molar ratio of the bisphenol diglycidyl ether compound to the dicarboxylic acid compound is 1: (2.0-4.0); the molar ratio of the triethylamine to the bisphenol diglycidyl ether compound is greater than or equal to 0.1; the temperature of the ring-opening reaction of the epoxy group is 55 DEG C or above. The invention further designs the phenoxy resin prepared by the preparation method and toughening application thereof. According to the method, phenoxy resin can be successfully synthesized, and the toughening effect of a bisphenol diglycidyl ether curing product can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a new method for preparing phenoxy resin from dicarboxylic acid and bisphenol epoxy resin and application of the phenoxy resin as a toughening agent. Background Art

[0002] Bisphenol diglycidyl ether compounds, such as the common bisphenol A diglycidyl ether compounds, are an important class of organic synthesis intermediates. In addition, due to their special chemical structure, they are widely used in the preparation of composite materials, optoelectronic materials, new energy materials and fine chemicals.

[0003] Since the epoxy functional group in bisphenol A diglycidyl ether compounds has high reactivity, it is very easy to undergo a ring-opening reaction under acidic or alkaline conditions. Usually, the epoxy functional group will form a new hydroxyl functional group after the ring opening. Due to the difference in reaction conditions, the hydroxyl functional group will continue to attack the epoxy functional group, thereby forming a corresponding ring-opening product with n>1. In the above reaction system, the corresponding phenoxy resin can be obtained by adding a suitable catalyst and controlling the reaction conditions.

[0004] Epoxy resin has a large number of epoxy groups in its structure, and the chemical crosslinking density of the cured structure is high, the molecular chain flexibility is low, and the internal stress is large, which leads to the brittleness of the cured material, poor impact resistance and fatigue durability, which limits its application and development in some high-tech fields that require high durability and reliability. Therefore, it is necessary to modify the toughness of epoxy resin while maintaining its excellent performance.

[0005] The methods of toughening with bisphenol A diglycidyl ether compounds reported in the literature mainly include: (1) adding rubber elastomers, core-shell polymers, thermoplastic resins, thermotropic liquid crystal polymers and nanoparticles to the epoxy resin matrix to form a microscopic phase separation or homogeneous structure; (2) continuously penetrating the thermoplastic resin into the three-dimensional cross-linked network of the epoxy resin to form an interpenetrating network structure for toughening; (3) adjusting the microstructure of the epoxy resin, such as introducing more flexible chain segments into the three-dimensional cross-linked network to improve its molecular flexibility, or introducing a microscopic phase separation structure to enhance the deformation synergy of the molecular chain segments to achieve toughening.

[0006] In 2015, Professor Ren Yanyu of Dalian University of Technology announced the method of "a composite toughened bisphenol A epoxy resin rebar embedding adhesive with strong bonding ability in high temperature environment and preparation method", with application number: CN201510168727.5. Although the above patent reported a new toughening method based on bisphenol A epoxy resin, its principle is still to use modified nitrile rubber as a toughening agent, with an addition ratio of more than 20%.

[0007] So far, the technology of modifying and toughening bisphenol A diglycidyl ether compounds based on phenoxy resin has not been reported, and the efficient synthesis of bisphenol A-based phenoxy resin has several problems such as raw material quality, production safety, and product stability and purity. The synthesis technology is relatively difficult. Currently, only a few companies in the United States, Japan, Germany and other countries are producing it, and some of my country's high-performance bisphenol A diglycidyl ether compound products currently rely mainly on imports.

[0008] In view of the shortcomings of the existing high-performance synthesis process of bisphenol A diglycidyl ether compounds, the industry is focusing on studying the use of mild reaction conditions and efficient catalysis to develop a new method for synthesizing the corresponding bisphenol A-based phenoxy resin using stable, inexpensive and readily available bisphenol A diglycidyl ether and dibasic acid compounds as building blocks, and then using it as an auxiliary agent to modify and toughen the bisphenol A diglycidyl ether compound. Summary of the invention

[0009] In view of the defects of existing bisphenol A diglycidyl ether compound solidified materials such as large brittleness, poor impact resistance and fatigue durability, the first purpose of the present invention is to provide a method for preparing a phenoxy resin toughening agent, aiming to prepare a phenoxy resin toughening agent that can effectively improve the toughness of bisphenol A diglycidyl ether compound solidified materials.

[0010] The second purpose of the present invention is to provide a phenoxy resin toughening agent prepared by the preparation method and its application as a toughening agent.

[0011] The third object of the present invention is to provide a cured material toughened by the phenoxy resin toughening agent.

[0012] A preparation method of a phenoxy resin toughening agent, comprising subjecting a bisphenol diglycidyl ether compound and a polyacid compound to an epoxy ring-opening reaction under the action of triethylamine to obtain the toughening agent;

[0013] The molar ratio of the bisphenol diglycidyl ether compound to the dicarboxylic acid compound is 1:2.0-4.0;

[0014] The molar ratio of triethylamine to the bisphenol diglycidyl ether compound is greater than or equal to 0.1;

[0015] The temperature of the epoxy ring-opening reaction is above 55°C.

[0016] The present invention provides a solvent-free phenoxy resin synthesis method, which innovatively adopts triethylamine as a catalyst and can achieve synergy based on the combined control of the catalyst dosage and the reaction temperature, and can effectively regulate the structure of the product, improve the yield and selectivity of the target structure, and facilitate the acquisition of a liquid phenoxy resin product. Moreover, the study also found that the product obtained under the preparation process and conditions can be used as a toughening agent to solve the problems of bisphenol diglycidyl ether compound solidified materials having high brittleness, poor impact resistance and fatigue resistance.

[0017] In the present invention, the bisphenol diglycidyl ether compound is a compound having the structural formula 1;

[0018]

[0019] In Formula 1, R1 and R2 are independently H, C1-C6 alkyl, C1-C6 alkoxy, halogen, nitro or trifluoromethyl;

[0020] Preferably, the bisphenol diglycidyl ether compound is a bisphenol A diglycidyl ether compound.

[0021] Preferably, the polyacid compound is a dicarboxylic acid compound, and a further preferred structural expression is HOOC-R-COOH, wherein R is selected from a benzene ring, a five-membered alkane ring, a six-membered alkane ring or a C1-C10 alkylene group;

[0022] More preferably, the dicarboxylic acid compound is one of terephthalic acid, phthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid, 1,2-cyclohexyldicarboxylic acid, 1,3-cyclohexyldicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

[0023] In the present invention, the amount of the polyacid compound is not less than the theoretical reaction amount. Considering the processing cost, the molar ratio of the bisphenol diglycidyl ether compound to the polyacid compound is preferably 1:2 to 2.5.

[0024] In the present invention, triethylamine is used as a catalyst to successfully prepare the phenoxy resin, improve its selectivity and yield, and improve the toughening effect of the prepared product on the bisphenol diglycidyl ether compound-based resin. Research has also found that further controlling the amount of triethylamine and the reaction temperature is helpful to synergistically improve the preparation effect and improve the toughening effect of the prepared material on the bisphenol diglycidyl ether compound-based resin.

[0025] Preferably, the molar amount of the organic amine catalyst is 0.1 to 0.3 times, more preferably 0.15 to 0.25 times, of the bisphenol diglycidyl ether compound.

[0026] In the present invention, the temperature of the epoxy ring-opening reaction is 60 to 100°C, preferably 70 to 100°C, and more preferably 75 to 90°C.

[0027] In the present invention, the time of the ring-opening reaction is 2 hours or more, preferably 3 to 15 hours, and more preferably 6 to 12 hours.

[0028] The invention also provides a phenoxy resin toughening agent prepared by the preparation method.

[0029] The invention also provides an application of the phenoxy resin toughening agent prepared by the preparation method, which is used as a toughening agent.

[0030] The preferred application of the present invention is to use it as a toughening agent to participate in the curing reaction of bisphenol diglycidyl ether compounds to prepare toughened resins.

[0031] Preferably, the bisphenol diglycidyl ether compound is the compound of formula 1.

[0032] A further preferred application of the present invention is to subject the raw materials comprising bisphenol diglycidyl ether compound, diacid precursor, curing accelerator and the toughening agent to a curing reaction to obtain a toughened resin;

[0033] Preferably, the diacid precursor is an acid anhydride, more preferably methyltetrahydrophthalic anhydride;

[0034] Preferably, the weight ratio of each component in the raw material is:

[0035]

[0036] In the present invention, the phenoxy resin toughening agent can be compounded with a bisphenol diglycidyl ether compound in advance, and then mixed with other ingredients for curing.

[0037] Preferably, the weight ratio of each component in the raw material is:

[0038]

[0039] The invention also provides a toughened resin obtained by the application of the invention.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) The preparation method of the phenoxy resin toughening agent of the present invention is simple and easy, the reaction conditions are mild, the process is easy to control, and it is safe and reliable. The substrate has wide applicability, no need to add additional organic solvents, high atom economic benefits, and no environmental pollution. The reaction efficiency is high, the yield is high, the selectivity is good, the reaction time is short, the impurities are small, the cost is low, it is suitable for large-scale production, and has good industrial application prospects.

[0042] (2) The prepared phenoxy resin toughening agent is innovatively used as a toughening component for the cured product of bisphenol A diglycidyl ether compound, which can solve the defects of the cured product such as high brittleness, poor impact resistance and fatigue durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 The H-NMR graph of the phenoxy resin prepared by using TEA as the organic amine prepared in Example 1;

[0044] Figure 2 The C-NMR graph of the phenoxy resin prepared by using TEA as the organic amine prepared in Example 1; DETAILED DESCRIPTION

[0045] In the following cases, the molar amount of the organic base added refers to the molar percentage relative to bisphenol A diglycidyl ether.

[0046] In the present invention, the bisphenol diglycidyl ether compound can be any bisphenol diglycidyl ether known in the industry. In the following cases, the bisphenol diglycidyl ether compound is typically exemplified by typical bisphenol A diglycidyl ether:

[0047] The typical preparation method of bisphenol A-based phenoxy resin of the present invention comprises the following steps: mixing bisphenol A diglycidyl ether with a diacid carboxylic acid compound, and performing an epoxy ring-opening reaction under the action of an organic amine catalyst to obtain the phenoxy resin.

[0048] The dicarboxylic acid compound has a structural expression of HOOC-R-COOH, wherein R is selected from one of benzene diyl, cyclohexyl, methylene, ethylene, propylene, butylene, pentylene, hexylene, and heptylene. The reaction expression of the catalyst (organic amine catalyst) of bisphenol A diglycidyl ether and the dicarboxylic acid compound is shown in the following formula (1).

[0049]

[0050] The dicarboxylic acid compound is one of terephthalic acid, phthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid, 1,2-cyclohexyldicarboxylic acid, 1,3-cyclohexyldicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

[0051] The organic amine catalyst is at least one of triethylamine, 1,8-diazabicycloundec-7-ene, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylbenzylamine, N,N-dibenzylaniline, diisopropylethylamine, N-phenylpiperidine, and N-ethyl-N-benzylaniline. The preferred organic amine catalyst not only allows the epoxy ring-opening reaction between bisphenol A diglycidyl ether and dicarboxylic acid compounds to be carried out at a lower temperature, but also has the characteristics of high conversion rate and high selectivity, and can avoid the use of solvents.

[0052] The molar ratio of the bisphenol A diglycidyl ether compound to the dicarboxylic acid compound is 1:2.0-4.0.

[0053] The molar ratio of the bisphenol A diglycidyl ether compound to the organic amine catalyst is 1:0.05-0.3. If the proportion of the organic amine used is too low, less than 5% of the bisphenol A diglycidyl ether, the selectivity of the reaction and the yield of the target product will be significantly reduced. When the organic amine is increased by 20% of the bisphenol A diglycidyl ether, the yield and selectivity of the target product reach the best. When the organic amine content is further increased, the yield and selectivity of the target product are appropriately reduced. Therefore, the molar ratio of bisphenol A diglycidyl ether to the organic amine catalyst is further preferably 1:0.1-0.3.

[0054] The ring-opening reaction conditions are: under nitrogen protection, the reaction temperature is 55-100° C., and the time is 3-15 hours. The further preferred reaction temperature is 60-100° C., and the most preferred is 70-90° C. Within the preferred temperature and time range, appropriately increasing the reaction temperature and extending the reaction time are beneficial to increasing the yield of the target product, but too high a reaction temperature and reaction time will increase the impact of side reactions.

[0055] A typical toughening step of the present invention is, for example, adding the prepared phenoxy resin to the bisphenol A diglycidyl ether compound according to a mass ratio and mixing them evenly. The mass ratio of the bisphenol A diglycidyl ether compound to the phenoxy resin is 1:0.001-0.1, and more preferably 1:0.001-0.05.

[0056] In the following cases, the tensile strength, bending strength, and impact tests are all tested using conventional industry standards, such as the national standard: GB / T 9341-2008 / ISO 178:2001.

[0057] In the present invention, in the following cases, the product selectivity is: the proportion of ordered polyester compounds formed by carboxyl groups selectively attacking the epoxy groups in bisphenol A diglycidyl ether.

[0058] In the following cases, the molar percentage of triethylamine added is based on the molar amount of bisphenol A diglycidyl ether.

[0059] Example 1

[0060] Prepare a set of parallel reactions, add 340 mg (1 mmol) of bisphenol A diglycidyl ether and 320 mg (2 mmol) of pimelic acid into Schlenk tubes under nitrogen protection, then add 20 mol% of organic base (triethylamine, 1,8-diazabicycloundec-7-ene, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylbenzylamine, N,N-dibenzylaniline, diisopropylethylamine, N-phenylpiperidine, N-ethyl-N-benzylaniline) into each Schlenk tube, stir and react at 80°C for 6 hours to obtain pimelic acid-modified phenoxy resin. HPLC and GC-MS chromatography showed that when triethylamine was used as the base, the yield and selectivity of the target product were the highest, with a selectivity of 96% and a yield of 93%. Other amines had poor catalytic effects, and the cured products were hard, and the nuclear magnetic resonance could not be measured, and the selectivity could not be calculated.

[0061] The NMR data are as follows: 1 H NMR (400MHz, CDCl3) δ7.05(m,4H),6.80-6.65(m,4H),4.27-4.01(m,6H),3.97-3.76(m,4H),3.00( q,J=7.3Hz,1H),2.33-2.14(m,8H),1.67-1.47(m,14H),1.37-1.23(m,4H),1.16(t,J=7.3Hz,2H). 13 C NMR (101MHz, CDCl3) δ178.84,173.81,156.17,143.77,127.79,113.96,68.63,68.53,65.26,45 .00,41.73,34.06,33.88,33.83,30.98,30.96,28.38,28.33,24.50,24.46,24.41,24.35,8.41.

[0062] Example 2

[0063] Prepare a set of parallel reactions, add 340mg (1mmol) of bisphenol A diglycidyl ether and 320mg (2mmol) of pimelic acid into Schlenk tubes under nitrogen protection, then add triethylamine (0mol%, 1mol%, 5mol%, 10mol%, 15mol%, 20mol%, 30mol%) in different molar ratios into each Schlenk tube, and stir and react at 80°C for 12 hours. HPLC and GC-MS analysis show that when the amount of triethylamine added is 20mol%, the yield and selectivity of the target product are the highest, with a selectivity of 97% and a yield of 94%. The specific data of other parallel experiments with different molar ratios of triethylamine addition are as follows: 0 mol% (selectivity is 60%, yield is 3%), 1 mol% (selectivity is 85%, yield is 22%), 5 mol% (selectivity is 88%, yield is 56%), 10 mol% (selectivity is 93%, yield is 87%), 20 mol% (selectivity is 96%, yield is 93%), 30 mol% (selectivity is 92%, yield is 85%).

[0064] Example 3

[0065] Prepare a set of parallel reactions, add 340mg (1mmol) of bisphenol A diglycidyl ether and 320mg (2mmol) of pimelic acid into Schlenk tubes under nitrogen protection, then add 20mol% of triethylamine into each Schlenk tube, and stir the reaction at 25℃, 40℃, 60℃, 80℃ and 100℃ for 12 hours to obtain pimelic acid-modified phenoxy resin. The results of the analysis by high performance liquid chromatography and gas chromatography-mass spectrometry are as follows: (25℃, selectivity is 98%, yield is 5%; 40℃, selectivity is 98%, yield is 22%; 60℃, selectivity is 97%, yield is 75%; 100℃, selectivity is 91%, yield is 88%;)

[0066] Example 4

[0067] Compared with the TEA experimental group in Example 1, the only difference is that sebacic acid or malonic acid is used to replace the pimelic acid, and the other operations and parameters are the same as in Example 1.

[0068] The experimental results are as follows: the product selectivity of the sebacic acid-modified phenoxy resin group is 97% and the yield is 90%;

[0069] The product selectivity of the malonic acid-modified phenoxy resin group was 95% and the yield was 91%;

[0070] Curing experiment operation steps:

[0071] Formula: Bisphenol A diglycidyl ether (100 parts) + methyltetrahydrophthalic anhydride (88 parts) + curing accelerator (2 parts) + toughening agent (X parts); a mixture of bisphenol A-based phenoxy resin + bisphenol A diglycidyl ether is used as a toughening agent;

[0072] The curing accelerators are all well-known ingredients in the industry. For example, in the following cases, unless otherwise stated, they all refer to N,N-dimethylbenzylamine.

[0073] After adding according to the formula, stir it, and put it into the defoaming bucket for 20-30 minutes, until there are no bubbles visible to the naked eye. After defoaming, pour it into the mold that has been preheated and sprayed with release agent, and put the mold into the oven. Curing at 100℃ for 1h, then heat it to 140℃ for 3h.

[0074] Comparative Example 1

[0075] Prepare a curing mold, and cure 100g of bisphenol A diglycidyl ether, 88g of methyltetrahydrophthalic anhydride and 2g of curing accelerator according to the above operation. After obtaining the cured model, the mechanical properties are tested respectively. The obtained data are as follows: tensile strength 77.86MPa, flexural strength 124.37MPa, impact test result 27.52KJ / m 2 The experimental data measured are blank control experiments.

[0076] Application Example 1

[0077] Prepare a curing mold, and respectively cure 100g of bisphenol A diglycidyl ether, 88g of methyltetrahydrophthalic anhydride, 2g of a curing accelerator and a toughening agent (10g, pimelic acid-modified phenoxy resin (Example 3, 80°C condition): bisphenol A diglycidyl ether mass ratio = 1:1) according to the above operation. After obtaining a cured model, mechanical properties tests were performed respectively. The obtained data are as follows: tensile strength 76.13MPa, flexural strength 77.85MPa, impact test result 33.35KJ / m 2 .

[0078] Application Example 2

[0079] Prepare a curing mold, and respectively cure 100g of bisphenol A diglycidyl ether, 88g of methyltetrahydrophthalic anhydride, 2g of a curing accelerator and a toughening agent (10g, pimelic acid-modified phenoxy resin (Example 3, 80°C condition): bisphenol A diglycidyl ether mass ratio = 9:1) according to the above operation. After obtaining a cured model, mechanical properties tests were performed respectively. The obtained data are as follows: tensile strength 80.58MPa, flexural strength 129.97MPa, impact test result 33.95KJ / m 2 .

[0080] Application Example 3

[0081] Prepare a curing mold, and respectively cure 100g of bisphenol A diglycidyl ether, 88g of methyltetrahydrophthalic anhydride, 2g of a curing accelerator and a toughening agent (5g, pimelic acid-modified phenoxy resin (Example 3, 80°C condition): bisphenol A diglycidyl ether mass ratio = 1:9) according to the above operation. After obtaining a cured model, mechanical properties tests were performed respectively. The obtained data are as follows: tensile strength is 84.61MPa, flexural strength is 151.46MPa, and impact test results are 36.2KJ / m 2 .

[0082] Application Example 4

[0083] Prepare a curing mold, and cure 100g of bisphenol A diglycidyl ether, 88g of methyltetrahydrophthalic anhydride, 2g of curing accelerator and toughening agent (5g, sebacic acid-modified phenoxy resin: bisphenol A diglycidyl ether mass ratio = 1:9) according to the above operation. After obtaining the cured model, the mechanical properties are tested respectively. The obtained data are as follows: tensile strength is 79.61MPa, flexural strength is 139.05MPa, and impact test result is 33.1KJ / m 2 .

[0084] Application Example 5

[0085] Prepare a curing mold, and cure 100g of bisphenol A diglycidyl ether, 88g of methyltetrahydrophthalic anhydride, 2g of curing accelerator and toughening agent (10g, malonic acid modified phenoxy resin: bisphenol A diglycidyl ether mass ratio = 1:9) according to the above operation. After obtaining the cured model, the mechanical properties are tested respectively. The obtained data are as follows: tensile strength is 84.11MPa, flexural strength is 145.84MPa, and impact test result is 33.7KJ / m 2 .

[0086] It can be seen from the above examples that the method adopted by the present invention of preparing the corresponding phenoxy resin by efficiently reacting bisphenol A diglycidyl ether with dicarboxylic acid compounds, and then mixing with bisphenol A diglycidyl ether to selectively toughen it has the advantages of mild reaction conditions, cheap and easy catalyst, high regional selectivity, etc. In addition, the method also has the advantages of wide substrate applicability and high yield, and provides a method for efficiently synthesizing bisphenol A-based phenoxy resins containing different substituted functional groups.

[0087] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a phenoxy resin toughening agent, characterized in that: The bisphenol diglycidyl ether compound and the polyacid compound are subjected to epoxy ring-opening reaction under the action of triethylamine to obtain; The molar ratio of the bisphenol diglycidyl ether compound to the dicarboxylic acid compound is 1:2.0-4.0; The molar ratio of triethylamine to the bisphenol diglycidyl ether compound is greater than or equal to 0.1; The temperature of the epoxy ring-opening reaction is above 55°C.

2. The method for preparing a phenoxy resin toughening agent according to claim 1, wherein: The bisphenol diglycidyl ether compound is a compound having the structural formula 1; In Formula 1, R1 and R2 are independently H, C1-C6 alkyl, C1-C6 alkoxy, halogen, nitro or trifluoromethyl; Preferably, the bisphenol diglycidyl ether compound is a bisphenol A diglycidyl ether compound.

3. The method for preparing a phenoxy resin toughening agent according to claim 1, wherein: The polyacid compound is a dicarboxylic acid compound, and the preferred structural expression is HOOC-R-COOH, wherein R is selected from a benzene ring, a five-membered alkane ring, a six-membered alkane ring or a C1-C10 alkylene group; More preferably, the dicarboxylic acid compound is one of terephthalic acid, phthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid, 1,2-cyclohexyldicarboxylic acid, 1,3-cyclohexyldicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

4. The method for preparing a phenoxy resin toughening agent according to any one of claims 1 to 3, characterized in that: The molar ratio of the bisphenol diglycidyl ether compound to the polyacid compound is 1:2 to 2.

5.

5. The method for preparing a phenoxy resin toughening agent according to claim 1, wherein: The molar amount of triethylamine is 0.1 to 0.3 times, preferably 0.15 to 0.25 times, the molar amount of the bisphenol diglycidyl ether compound.

6. The method for preparing a phenoxy resin toughening agent according to claim 1, wherein: The temperature of the epoxy ring-opening reaction is 60 to 100°C, preferably 70 to 100°C, and more preferably 75 to 90°C.

7. The method for preparing a phenoxy resin toughening agent according to claim 1, wherein: The ring-opening reaction time is more than 2 hours, preferably 3 to 15 hours.

8. A phenoxy resin toughening agent prepared by the preparation method according to any one of claims 1 to 7.

9. An application of a phenoxy resin toughening agent prepared by the preparation method according to any one of claims 1 to 7, characterized in that: As a toughening agent.

10. The use according to claim 9, characterized in that It is used as a toughening agent to participate in the curing reaction of bisphenol diglycidyl ether compound to prepare toughened resin; Preferably, the bisphenol diglycidyl ether compound is the compound of formula 1 as claimed in claim 2.

11. The use according to claim 9 or 10, characterized in that: The raw materials including bisphenol diglycidyl ether compound, diacid precursor, curing accelerator and toughening agent are subjected to curing reaction to obtain toughened resin; Preferably, the diacid precursor is an acid anhydride, more preferably methyltetrahydrophthalic anhydride; Preferably, the weight ratio of each component in the raw material is:

12. A toughened resin obtained by the use according to claim 10 or 11.

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