Hyperbranched epoxy resin modified MBS toughening agent and preparation method thereof

Abstract

The invention relates to the technical field of toughening agents, in particular to a hyperbranched epoxy resin modified MBS toughening agent and a preparation method thereof.The preparation method comprises the following steps that (S1) a cyclotriazine compound, polyglycidyl ether and a catalyst are added into an organic solvent to be mixed, a reaction is conducted for 8-72 h at the temperature of 30-150 DEG C under the protection of nitrogen, and after the reaction is completed, alcohol precipitation and drying are conducted to obtain a hyperbranched epoxy resin modified MBS toughening agent; the hyperbranched epoxy resin is obtained; (S2) adding the hyperbranched epoxy resin into the solvent A, uniformly mixing, then adding MBS resin, stirring for 0.5-1 hour at a high speed under the condition of room temperature, then heating to 70-110 DEG C, stirring for 0.5-1 hour, and removing the residual solvent to obtain the hyperbranched epoxy resin modified MBS toughening agent, and by utilizing the hyperbranched characteristic of the resin, enabling the modified MBS toughening agent to be used for preparing the hyperbranched epoxy resin modified MBS toughening agent. The toughening effect can be achieved by adding a small amount of the toughening agent into common epoxy resin.

Description

Technical Field

[0001] The invention relates to the technical field of toughening agents, and in particular to a hyperbranched epoxy resin-modified MBS toughening agent and a preparation method thereof. Background Art

[0002] Epoxy resin refers to a polymer compound containing two or more epoxy groups in the molecule, with aliphatic, alicyclic or aromatic chain segments as the skeleton. Under appropriate curing conditions, such as amine, imidazole, acid anhydride or phenolic resin, it can form a three-dimensional cross-linked network of cured polymers. After curing, epoxy resin has a high cross-linking density and high strength, and is widely used in many fields.

[0003] Since epoxy resin forms a three-dimensional network structure macromolecule after curing, the movement of the main chain of the molecule is restricted, the internal stress is large, and it is easy to become brittle, resulting in low impact strength, low peel strength, poor fatigue resistance, low fracture toughness coefficient, and easy cracking. In order to solve the above problems of epoxy resin, toughening agents are usually added to the epoxy resin system to improve the toughness of the epoxy resin cured product.

[0004] At present, the main toughening methods for epoxy resins include adding rubber elastomers, thermotropic liquid crystal polymers, inorganic nanoparticles, core-shell polymer toughening, etc., which are mainly achieved by adjusting the crosslinking density of the epoxy resin. The solution with patent publication number CN104725782A is to use one or more of carboxylated nitrile elastic nanoparticles, nitrile elastic nanoparticles, carboxylated butadiene styrene elastic nanoparticles, butadiene styrene pyridine elastic nanoparticles to toughen and modify the epoxy resin, but the synthesis process often has many steps, high production costs, and insufficient toughening effect. Summary of the invention

[0005] In order to overcome the shortcomings and deficiencies in the prior art, one of the purposes of the present invention is to provide a method for preparing a hyperbranched epoxy resin modified MBS toughening agent, using cyclotriazine compounds and polyglycidyl ethers as raw materials, catalyzing and synthesizing a hyperbranched epoxy resin in one step, having good solubility of hyperbranched polymers and a large number of active epoxy end groups, and then modifying with MBS resin, hyperbranched epoxy resin can directly dissolve MBS resin and completely coat it under the condition of solvent A, synthesizing a toughening modifier with good toughening effect suitable for epoxy resin toughening, the process of the present invention is simple, efficient, the product is easy to purify, and the product is highly stable. The preparation method is simple to operate, convenient to control, high in production efficiency, low in production cost, and can be used for large-scale production.

[0006] The second object of the present invention is to provide a hyperbranched epoxy resin modified MBS toughening agent, which utilizes the hyperbranching characteristics of the resin to achieve a toughening effect when added in a low amount in ordinary epoxy resin.

[0007] One of the purposes of the present invention is achieved by the following technical solution: A method for preparing a hyperbranched epoxy resin modified MBS toughening agent comprises the following steps:

[0008] (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 30-150° C. for 8-72 hours under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin;

[0009] (S2), adding the hyperbranched epoxy resin to solvent A and mixing evenly, then adding MBS resin, stirring at high speed for 0.5-1h at room temperature, then heating to 70-110°C, stirring for 0.5-1h, removing the remaining solvent, and obtaining a hyperbranched epoxy resin modified MBS toughening agent.

[0010] The synthesis of existing hyperbranched epoxy resins usually requires the addition of a large amount of organic solvents. After the reaction is completed, most processes require a water washing step, which has certain pollution to the environment, harsh reaction conditions, and low yield. The preparation method of the MBS toughening agent of the present invention uses cyclotriazine compounds and polyglycidyl ethers as raw materials to catalyze the one-step synthesis of hyperbranched epoxy resins. It has good solubility of hyperbranched polymers and a large number of active epoxy end groups. The process is simple, the product is easy to purify, and the efficiency is higher. In addition, MBS resin is solid and cannot be directly added to epoxy resin for direct use. Due to the difference in the chemical structure of MBS resin and epoxy resin, the compatibility between them is not ideal. Therefore, direct mixing will lead to problems of uneven dispersion and performance degradation. The preparation method of the MBS toughening agent of the present invention uses hyperbranched epoxy resin in the presence of solvent A to directly dissolve MBS resin and completely coat it. The synthesized MBS toughening agent has good toughening effect and is suitable for epoxy resin toughening. Low addition amount in ordinary epoxy resin can achieve excellent toughening effect. Preferably, the MBS resin is MBS resin powder, such as commercially available Japan Kabushiki M732, Japan Kabushiki M711, and Rohm and Haas EXL2620.

[0011] Preferably, in the step (S1), the weight percentage of each raw material used is 1-20 parts of cyclotriazine compound, 1-30 parts of polyglycidyl ether, 0.5-5 parts of catalyst, and 11-65 parts of organic solvent.

[0012] Preferably, in the step (S2), the weight portions of the raw materials used are 50-80 parts of the hyperbranched epoxy resin, 40-80 parts of the solvent A, and 20-50 parts of the MBS resin.

[0013] Preferably, the structural formula of the cyclotriazine compound is

[0014]

[0015] Wherein, R1 is -C6H4(CH2) n -or-CH2(CH2) m -, wherein n = 1, 2, 3 or 4, m = 2, 3, 4 or 5, the -C6H4(CH2) n -The benzene ring is substituted at the para, meta or ortho position, and the benzene ring structure is substituted by an amino group.

[0016] Preferably, the polyglycidyl ether is at least one of glycerol triglycidyl ether, ethylene glycol monoglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolpropane triglycidyl ether and trimethylolethane triglycidyl ether.

[0017] Preferably, the catalyst is at least one of potassium tert-butoxide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide, hexadecyltriethylammonium bromide, tetrabutylammonium chloride, sodium hydroxide, and 18-crown-6 complex potassium hydroxide.

[0018] Preferably, the organic solvent is at least one of tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, and ethylene glycol dibutyl ether.

[0019] Preferably, in the step (S1), the alcohol used in the alcohol precipitation treatment is ethanol or methanol.

[0020] Preferably, in the step (S2), the speed of high-speed stirring is 500-1500 r / min, and the solvent A is at least one of butanone, toluene, ethyl acetate, and propylene glycol methyl ether.

[0021] The second object of the present invention is achieved by the following technical solution: a hyperbranched epoxy resin modified MBS toughening agent is prepared by the preparation method of the hyperbranched epoxy resin modified MBS toughening agent.

[0022] The beneficial effects of the present invention are as follows: the preparation method of the hyperbranched epoxy resin modified MBS toughening agent of the present invention uses cyclotriazine compounds and polyglycidyl ethers as raw materials, catalyzes the one-step synthesis of hyperbranched epoxy resin, has good solubility of hyperbranched polymers, and has a large number of active epoxy end groups, and then is modified with MBS resin. The hyperbranched epoxy resin can directly dissolve the MBS resin and completely coat it under the condition of the presence of solvent A, and synthesizes a toughening modifier with good toughening effect and suitable for epoxy resin toughening. The process of the present invention is simple, efficient, and the product is easy to purify and the product is highly stable. The preparation method is simple to operate, convenient to control, high in production efficiency, low in production cost, and can be used for large-scale production.

[0023] The hyperbranched epoxy resin modified MBS toughening agent of the present invention utilizes the hyperbranching characteristics of the resin so that the modified MBS toughening agent can achieve toughening effect with a low addition amount in common epoxy resin. DETAILED DESCRIPTION

[0024] In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments, and the contents mentioned in the implementation modes are not intended to limit the present invention.

[0025] Example 1

[0026] A method for preparing a hyperbranched epoxy resin modified MBS toughening agent comprises the following steps:

[0027] (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 60° C. for 24 hours under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin;

[0028] (S2), add the hyperbranched epoxy resin to solvent A and mix evenly, then add MBS resin powder (commercially available Japan Kanebashi M732), stir at high speed for 0.5h at room temperature, then heat to 80°C and stir for 1h, remove the remaining solvent, and obtain a hyperbranched epoxy resin modified MBS toughening agent.

[0029] In the step (S1), the weight ratio of each raw material used is 20 parts of cyclotriazine compound, 25 parts of polyglycidyl ether, 3 parts of catalyst, and 50 parts of organic solvent.

[0030] In the step (S2), the weight portions of the raw materials used are 80 parts of hyperbranched epoxy resin, 50 parts of solvent A, and 20 parts of MBS resin powder.

[0031] The structural formula of the cyclotriazine compound is

[0032]

[0033] Wherein, R1 is -C6H4(CH2) n -, wherein n = 1, said -C6H4(CH2) n -The benzene ring is substituted at the meta position and the benzene ring structure is substituted by amino group.

[0034] The polyglycidyl ether is pentaerythritol triglycidyl ether.

[0035] The catalyst is tetrabutylammonium chloride.

[0036] The organic solvent is N,N-dimethylformamide.

[0037] In the step (S1), the alcohol used in the alcohol precipitation treatment is ethanol.

[0038] In the step (S2), the speed of high-speed stirring is 1000 r / min, and the solvent A is butanone.

[0039] Example 2

[0040] A method for preparing a hyperbranched epoxy resin modified MBS toughening agent comprises the following steps:

[0041] (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 120° C. for 48 hours under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin;

[0042] (S2), add the hyperbranched epoxy resin to solvent A and mix evenly, then add MBS resin powder (commercially available Japan Kanebashi M711), stir at high speed for 0.5h at room temperature, then heat to 90°C and stir for 1h, remove the remaining solvent, and obtain a hyperbranched epoxy resin modified MBS toughening agent.

[0043] In the step (S1), the weight ratio of each raw material used is 20 parts of cyclotriazine compound, 26 parts of polyglycidyl ether, 3 parts of catalyst, and 63 parts of organic solvent.

[0044] In the step (S2), the weight portions of the raw materials used are 72 parts of hyperbranched epoxy resin, 65 parts of solvent A, and 28 parts of MBS resin powder.

[0045] The structural formula of the cyclotriazine compound is

[0046]

[0047] Wherein, R1 is -C6H4(CH2) n -, wherein n = 1, said -C6H4(CH2) n -The benzene ring is substituted at the meta position and the benzene ring structure is substituted by amino group.

[0048] The polyglycidyl ether is a mixture of trimethylolethane triglycidyl ether and pentaerythritol triglycidyl ether in a weight ratio of 74:100.

[0049] The catalyst is tetrabutylammonium hydroxide.

[0050] The organic solvent is dimethyl sulfoxide.

[0051] In the step (S1), the alcohol used in the alcohol precipitation treatment is methanol.

[0052] In the step (S2), the speed of high-speed stirring is 1200 r / min, and the solvent A is butanone.

[0053] Example 3

[0054] A method for preparing a hyperbranched epoxy resin modified MBS toughening agent comprises the following steps:

[0055] (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 40° C. for 72 hours under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin;

[0056] (S2), add the hyperbranched epoxy resin to solvent A and mix evenly, then add MBS resin powder (commercially available Japan Kanebashi M732), stir at high speed for 1 hour at room temperature, then heat to 90°C and stir for 1 hour, remove the remaining solvent, and obtain a hyperbranched epoxy resin modified MBS toughening agent.

[0057] In the step (S1), the weight ratios of the raw materials used are 10 parts of cyclotriazine compound, 19 parts of polyglycidyl ether, 1 part of catalyst and 38 parts of organic solvent.

[0058] In the step (S2), the weight portions of the raw materials used are 60 parts of hyperbranched epoxy resin, 75 parts of solvent A, and 40 parts of MBS resin powder.

[0059] The structural formula of the cyclotriazine compound is

[0060]

[0061] Wherein, R1 is -C6H4(CH2) n -, wherein n = 2, said -C6H4(CH2) n -The benzene ring is substituted at the meta position, and the benzene ring structure is substituted by amino group.

[0062] The polyglycidyl ether is trimethylolethane triglycidyl ether.

[0063] The catalyst is hexadecyltrimethylammonium bromide.

[0064] The organic solvent is tetrahydrofuran.

[0065] In the step (S1), the alcohol used in the alcohol precipitation treatment is methanol.

[0066] In the step (S2), the speed of high-speed stirring is 1300 r / min, and the solvent A is butanone.

[0067] Example 4

[0068] A method for preparing a hyperbranched epoxy resin modified MBS toughening agent comprises the following steps:

[0069] (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 80° C. for 12 h under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin;

[0070] (S2) Add the hyperbranched epoxy resin to solvent A and mix evenly, then add MBS resin powder (commercially available Rohm and Haas EXL2620), stir at high speed for 1 hour at room temperature, then heat to 90° C. and stir for 1 hour, remove the remaining solvent, and obtain a hyperbranched epoxy resin modified MBS toughening agent.

[0071] In the step (S1), the weight ratio of each raw material used is 20 parts of cyclotriazine compound, 11 parts of polyglycidyl ether, 3 parts of catalyst, and 30 parts of organic solvent.

[0072] In the step (S2), the weight portions of the raw materials used are 60 parts of hyperbranched epoxy resin, 75 parts of solvent A, and 40 parts of MBS resin powder.

[0073] The structural formula of the cyclotriazine compound is

[0074]

[0075] Wherein, R1 is -CH2(CH2) m -, where m=2.

[0076] The polyglycidyl ether is glycerol triglycidyl ether.

[0077] The catalyst is tetrabutylammonium chloride.

[0078] The organic solvent is dioxane.

[0079] In the step (S1), the alcohol used in the alcohol precipitation treatment is ethanol.

[0080] In the step (S2), the speed of high-speed stirring is 1300 r / min, and the solvent A is butanone.

[0081] Comparative Example 1

[0082] A preparation method of an MBS toughening agent comprises the following steps: taking 60 parts of epoxy resin E-51 and 75 parts of butanone by weight and mixing them evenly, adding 40 parts of MBS resin powder (commercially available Rohm and Haas EXL2620), mechanically stirring at a speed of 1300 r / min for 1 hour at room temperature, then heating to 80°C, stirring for 1 hour, removing excess butanone, and obtaining the MBS toughening agent.

[0083] Comparative Example 2

[0084] A method for preparing a hyperbranched epoxy resin comprises the following steps:

[0085] (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 60° C. for 24 hours under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin.

[0086] In the step (S1), the weight ratio of each raw material used is 20 parts of cyclotriazine compound, 25 parts of polyglycidyl ether, 3 parts of catalyst, and 50 parts of organic solvent.

[0087] The structural formula of the cyclotriazine compound is

[0088]

[0089] Wherein, R1 is -C6H4(CH2) n -, wherein n = 1, said -C6H4(CH2) n -The benzene ring is substituted at the meta position and the benzene ring structure is substituted by amino group.

[0090] The polyglycidyl ether is pentaerythritol triglycidyl ether.

[0091] The catalyst is tetrabutylammonium chloride.

[0092] The organic solvent is N,N-dimethylformamide.

[0093] In the step (S1), the alcohol used in the alcohol precipitation treatment is ethanol.

[0094] Performance Testing

[0095] The preparation method of a blank control sample comprises the following steps: taking 100 parts by weight of E51 epoxy resin, stirring it evenly, adding DDM curing agent (the stoichiometric ratio of epoxy group to active hydrogen is 1), and after complete dissolution, vacuum degassing is performed to obtain a modified epoxy resin; pouring the modified epoxy resin into a silicone mold, heating and curing it, cooling it to room temperature, and obtaining a modified epoxy resin cured product; wherein the curing conditions are heating to 50° C. and keeping it warm for 2 hours, then heating to 80° C. and keeping it warm for 3 hours, and then heating to 140° C. and keeping it warm for 3 hours.

[0096] The preparation method of the test sample comprises the following steps: taking 5 parts by weight of a toughening agent, adding 95 parts by weight of an E51 epoxy resin, stirring well, adding a DDM curing agent (the stoichiometric ratio of epoxy groups to active hydrogen is 1), and after complete dissolution, vacuum degassing is performed to obtain a modified epoxy resin; pouring the modified epoxy resin into a silicone mold, heating and curing it, and cooling it to room temperature to obtain a modified epoxy resin cured product; wherein the curing conditions are heating to 50° C. and keeping the temperature for 2 hours, then heating to 80° C. and keeping the temperature for 3 hours, and then heating to 140° C. and keeping the temperature for 3 hours, and the toughening agent is taken from the MBS toughening agent of Examples 1-4 and Comparative Example 1.

[0097] The preparation method of the comparative sample comprises the following steps: taking 5 parts by weight of a hyperbranched epoxy resin, adding 95 parts by weight of an E51 epoxy resin, stirring well, adding a DDM curing agent (the stoichiometric ratio of epoxy groups to active hydrogen is 1), and after complete dissolution, vacuum degassing to obtain a modified epoxy resin; pouring the modified epoxy resin into a silicone mold, heating and curing it, cooling it to room temperature, and obtaining a modified epoxy resin cured product; wherein the curing conditions are heating to 50° C. and keeping the temperature for 2 hours, then heating to 80° C. and keeping the temperature for 3 hours, and then heating to 140° C. and keeping the temperature for 3 hours, and the hyperbranched epoxy resin is taken from the hyperbranched epoxy resin of comparative example 2.

[0098] The mechanical properties of the blank control sample, the comparative sample, the test samples of each embodiment and the comparative example were tested, and the test results are shown in the table:

[0099]

[0100]

[0101] It can be seen from the above table that the impact strength and fracture toughness of the modified epoxy resin cured products of Examples 1-4 are greatly improved compared with the blank control sample, and the toughening effect is better than the epoxy resin cured product of Comparative Example 1 and the control sample.

[0102] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. A method for preparing a hyperbranched epoxy resin modified MBS toughening agent, characterized in that: The steps include: (S1), adding a cyclotriazine compound, a polyglycidyl ether and a catalyst to an organic solvent, reacting at 30-150° C. for 8-72 hours under nitrogen protection, precipitating with alcohol after the reaction, and drying to obtain a hyperbranched epoxy resin; (S2), adding the hyperbranched epoxy resin to solvent A and mixing evenly, then adding MBS resin, stirring at high speed for 0.5-1h at room temperature, then heating to 70-110°C, stirring for 0.5-1h, removing the remaining solvent, and obtaining a hyperbranched epoxy resin modified MBS toughening agent.

2. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: In the step (S1), the weight ratio of each raw material is 1-20 parts of cyclotriazine compound, 1-30 parts of polyglycidyl ether, 0.5-5 parts of catalyst, and 11-65 parts of organic solvent.

3. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: In the step (S2), the weight proportions of the raw materials are 50-80 parts of the hyperbranched epoxy resin, 40-80 parts of the solvent A, and 20-50 parts of the MBS resin.

4. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: The structural formula of the cyclotriazine compound is Wherein, R1 is -C6H4(CH2) n -or-CH2(CH2) m -, wherein n = 1, 2, 3 or 4, m = 2, 3, 4 or 5, the -C6H4(CH2) n -The benzene ring is substituted at the para, meta or ortho position, and the benzene ring structure is substituted by an amino group.

5. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: The polyglycidyl ether is at least one of glycerol triglycidyl ether, ethylene glycol monoglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolpropane triglycidyl ether and trimethylolethane triglycidyl ether.

6. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: The catalyst is at least one of potassium tert-butoxide, tetrabutylammonium hydroxide, hexadecyltrimethylammonium bromide, hexadecyltriethylammonium bromide, tetrabutylammonium chloride, sodium hydroxide, and 18-crown-6 complex potassium hydroxide.

7. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: The organic solvent is at least one of tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, and ethylene glycol dibutyl ether.

8. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: In the step (S1), the alcohol used in the alcohol precipitation treatment is ethanol or methanol.

9. The method for preparing a hyperbranched epoxy resin modified MBS toughening agent according to claim 1, characterized in that: In the step (S2), the speed of high-speed stirring is 500-1500 r / min, and the solvent A is at least one of butanone, toluene, ethyl acetate, and propylene glycol methyl ether.

10. A hyperbranched epoxy resin modified MBS toughening agent, characterized in that: The invention discloses a hyperbranched epoxy resin-modified MBS toughening agent according to any one of claims 1 to 9.

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