Methylcyclohexanediamine derivative, preparation method and application thereof

Abstract

The application discloses a methylcyclohexanediamine derivative, a preparation method and application thereof, and a structure formula of the methylcyclohexanediamine derivative is shown as formula I: formula I; wherein R1 is selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, ester, and tert-butyl. The methylcyclohexanediamine derivative provided by the application has high active hydrogen equivalent, and when the methylcyclohexanediamine derivative is applied as an epoxy resin curing agent, the aliphatic ring structure contained in the molecular structure provides rigidity and chemical corrosion resistance of a paint film after curing, has excellent bending resistance and flexibility, and well balances the rigidity and flexibility of the paint film after curing, and is a very ideal aliphatic amine curing agent.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alicyclic amine curing agent, in particular to a methylcyclohexanediamine derivative, a preparation method and application thereof. BACKGROUND

[0002] The methylcyclohexanediamine derivative is an oligomer with two or more than two epoxy groups in the molecule, and an aliphatic, alicyclic or aromatic carbon bond as the skeleton and can form a thermosetting resin through the reaction of the epoxy groups. It has good adhesion, electrical insulation, low shrinkage, chemical stability, high and low temperature resistance, wear resistance and other excellent properties, and is usually used as a resin matrix of adhesives, coatings and composites, and is widely used in the fields of construction, machinery, electronics, aerospace and the like.

[0003] Epoxy resin must be added with a curing agent when used. An excellent curing agent can endow the cured product of the epoxy resin with excellent properties. Through the curing reaction, the epoxy resin generates a product with a three-dimensional network structure, becoming an epoxy resin material with real use value.

[0004] Among the epoxy resin curing agents, amine curing agents are of various types, large in dosage and wide in application. Common amine epoxy resin curing agents mainly include aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents and polyamide curing agents. Among them, aliphatic amine curing agents (such as ethylenediamine and diethylenetriamine) have the disadvantages of large volatility, large toxicity, fast curing, too strict ratio, and the like, and can absorb carbon dioxide to reduce the curing effect; aromatic amine curing agents exist in solid form at room temperature, have certain toxicity, and have poor compatibility with epoxy resin, so they are less and less used in the field of medium and low temperature curing; polyamide curing agents have low heat resistance, with a heat distortion temperature of only about 50℃, and incomplete curing below 15℃, which makes the physical properties and mechanical properties of the cured product decrease, so a promoter must be added to adjust the curing speed, but excessive addition will cause the brittleness of the cured product to increase and the resistance to gasoline and hydrocarbon solvents to be poor. The alicyclic amine curing agent is an amine compound containing alicyclic (cyclohexyl, hetero oxygen, nitrogen atom six-membered ring) in the molecular structure. Most of them are low-viscosity liquids, have a longer trial period than aliphatic amine curing agents, have better color of the cured product than aliphatic amine curing agents and polyamide curing agents, can be cured at medium temperature, have good transparency and weather resistance, and have high mechanical strength of the cured product.

[0005] Common alicyclic amine curing agents include isophorone diamine, ortho-diamine cyclohexane and 4,4'-diaminodicyclohexyl methane, but they have the disadvantages of large heat release, low active hydrogen equivalent, easy volatilization, easy moisture absorption and whitening, etc. during curing, thus causing some components of the coating or curing agent to be lost before curing, making the performance of the product not as expected, and possibly causing the transparency of the product to decrease, especially in applications with high requirements for transparency, such as optical materials or transparent coatings.

[0006] Therefore, the prior art still needs to be improved and developed. SUMMARY

[0007] In view of the deficiencies of the prior art described above, the present application provides a methylcyclohexanediamine derivative, a preparation method and application thereof, so as to solve the problem that the rigidity, chemical corrosion resistance, bending resistance and flexibility of the paint film cured by the existing alicyclic amine curing agent cannot meet the requirements.

[0008] The technical scheme adopted by the present application to solve the above technical problems is as follows:

[0009] In a first aspect of the present application, a methylcyclohexanediamine derivative is provided, and the structural formula of the methylcyclohexanediamine derivative is shown as formula I:

[0010]

[0011] wherein R1 is selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, ester group and tert-butyl.

[0012] In a second aspect of the present application, a preparation method of the above methylcyclohexanediamine derivative is provided, and the preparation method comprises the following steps:

[0013] 4-methyl-1,3-cyclohexanediamine shown as formula II and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate shown as formula III are subjected to nucleophilic substitution reaction to obtain tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl) bis(nitrogen hetero-diyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate shown as formula IV; wherein R1 in formula III is selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, ester group and tert-butyl;

[0014] The tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl) bis(nitrogen hetero-diyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate shown as formula IV is subjected to deprotection treatment to obtain the methylcyclohexanediamine derivative shown as formula I;

[0015] The above reaction route is shown as follows:

[0016]

[0017] Preferably, the step of nucleophilic substitution reaction of 4-methyl-1,3-cyclohexane diamine as shown in Formula II and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate as shown in Formula III to obtain tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl)) tetraaminocarboxylate as shown in Formula IV, specifically comprises:

[0018] Mixing 4-methyl-1,3-cyclohexane diamine as shown in Formula II, di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate as shown in Formula III, a first solvent and a catalyst, and performing nucleophilic substitution reaction at 60-120℃ for 2-12h to obtain tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl)) tetraaminocarboxylate as shown in Formula IV.

[0019] Preferably, the equivalent ratio of 4-methyl-1,3-cyclohexane diamine and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is 1:(2-4).

[0020] Preferably, the ratio of the volume of the first solvent to the mass of 4-methyl-1,3-cyclohexane diamine and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is (2-10) mL:1g.

[0021] Preferably, the molar ratio of the catalyst to 4-methyl-1,3-cyclohexane diamine is (1.3-5):1.

[0022] Preferably, the step of deprotection of tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl)) tetraaminocarboxylate to obtain methylcyclohexane diamine derivative as shown in Formula I, specifically comprises:

[0023] After spinning dry the first solvent in the system after the nucleophilic substitution reaction, adding a second solvent and a deprotection agent to the tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl)) tetraaminocarboxylate, and after reacting at 30-80℃ for 1-3h, adding a deprotection neutralizing agent and drying the organic phase to obtain methylcyclohexane diamine derivative as shown in Formula I.

[0024] Preferably, the volume of the second solvent is 20%-150% of the volume of the first solvent.

[0025] The first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, 1,2-dichloroethane, and the second solvent is selected from dichloromethane or chloroform.

[0026] The catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate.

[0027] Preferably, the deprotection agent is trifluoroacetic acid or dilute hydrochloric acid, and the deprotection neutralizing agent is selected from one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide.

[0028] In a third aspect of the present application, the methylcyclohexanediamine derivative is used for curing epoxy resin.

[0029] Advantages:

[0030] The present application discloses a methylcyclohexanediamine derivative, a preparation method and application thereof. DETAILED DESCRIPTION

[0031] The present application provides a methylcyclohexanediamine derivative, a preparation method and application thereof.

[0032] The present application provides a methylcyclohexanediamine derivative, a preparation method and application thereof.

[0033]

[0034] Preferably, R1 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, ester, and tert-butyl.

[0035] The methylcyclohexanediamine derivative provided by the embodiment of the present application contains a large number of amino groups, and the amino groups have the ability to form complexes with metal ions. Specifically, on a metal surface, the amino groups of the methylcyclohexanediamine derivative can form coordinate bonds with the metal to form a protective complex film, and such a complex film can prevent the metal from directly contacting oxygen, moisture, salt and the like in the environment, thereby slowing down the corrosion reaction of the metal. The amino groups can also provide more electrons to form an electron-rich region on the metal surface, slow down the oxidation reaction of the metal, and help to inhibit the corrosion and oxidation of the metal. In addition, the increase of the structure chain and the number of amino groups can improve the interaction of the methylcyclohexanediamine derivative with the metal surface, and such a change can help to improve the adhesion of the methylcyclohexanediamine derivative as a curing agent in a coating or lubricating oil, so that it is more firmly attached to the metal surface to form a more durable protective film. The increase of the structure chain can improve the viscosity and flowability of the methylcyclohexanediamine derivative as a curing agent in a liquid state due to the increase of the molecular size. Further, the increase of the structure chain can enhance the molecular stability and heat resistance of the methylcyclohexanediamine derivative as a curing agent, and it is not easy to decompose or fail.

[0036] On the other hand, from the perspective of molecular structure design modification, the volume of the substituent side group contained in the monomer structure of the methylcyclohexanediamine derivative is large, which is beneficial to improve the free volume of the polymer molecular chain prepared by using the aliphatic cyclic amine with super-large side group structure as a monomer, reduce the interaction between the molecular chains, and thus better improve the film-forming property and gas separation performance of the polymer, and the methylcyclohexanediamine derivative has a good application prospect in the preparation of special polymer film materials such as polyurethane.

[0037] In some embodiments, the methylcyclohexanediamine derivative can be one of the following structural formulas, but is not limited thereto:

[0038]

[0039] The embodiment of the present application provides a preparation method of the methylcyclohexanediamine derivative, and the preparation method comprises the following steps:

[0040] The nucleophilic substitution reaction is performed on 4-methyl-1,3-cyclohexanediamine shown in formula II and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate shown in formula III to obtain ((4-methylcyclohexane-1,3-diyl) bis(nitrogen hetero-diyl)) bis(2-substituted butane-4,1,1-triyl)) tetra-tert-butyl tetrakisaminoformate) shown in formula IV; wherein R1 in formula III is selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, ester group and tert-butyl.

[0041] Deprotection of tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl))tetramic acid as shown in formula IV, to obtain the methylcyclohexanediamine derivative as shown in formula I;

[0042] The above reaction route is as follows:

[0043]

[0044] The present application also provides a preparation method of the above-mentioned methylcyclohexanediamine derivative. The preparation method provided by the present application has a simple synthesis process route, uses cheap and easily available raw materials, and has the advantages of easy product purification and separation, high yield, stability at room temperature, low production cost, and suitability for industrial production.

[0045] In some embodiments, the formula III can be one of the following structural formulas, but is not limited thereto:

[0046]

[0047] In some embodiments, the formula IV can be one of the following structural formulas, but is not limited thereto:

[0048]

[0049]

[0050] In some embodiments, when R1 in formula III is hydrogen, the structural formula of formula III is The structural formula of formula IV is The structure of the methylcyclohexanediamine derivative is

[0051] In some embodiments, when R1 in formula III is hydrogen, the structural formula of formula III is The structural formula of formula IV is The reaction formula for preparing the methylcyclohexanediamine derivative is:

[0052]

[0053] In some embodiments, when R1 in formula III is methyl, the structural formula of formula III is The structural formula of formula IV is The structure of the methylcyclohexanediamine derivative is

[0054] When R1 in formula III is methyl, the structural formula of formula III is The structural formula of formula IV is The reaction formula for preparing the methylcyclohexanediamine derivative is:

[0055]

[0056] In some embodiments, the step of carrying out a nucleophilic substitution reaction of 4-methyl-1,3-cyclohexane diamine as shown in Formula II and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate as shown in Formula III to obtain tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl))tetraminocarbonate as shown in Formula IV specifically comprises:

[0057] Mixing 4-methyl-1,3-cyclohexane diamine as shown in Formula II, di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate as shown in Formula III, a first solvent and a catalyst, and carrying out a nucleophilic substitution reaction at 60-120°C for 2-12h to obtain tetra-tert-butyl (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl))tetraminocarbonate as shown in Formula IV.

[0058] In some embodiments, the equivalent ratio of the 4-methyl-1,3-cyclohexane diamine and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is 1:(2-4).

[0059] In some embodiments, the equivalent ratio of the 4-methyl-1,3-cyclohexane diamine and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is 1:(2-4).

[0060] In some preferred embodiments, the equivalent ratio of the 4-methyl-1,3-cyclohexane diamine and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is 1:(2.2-4).

[0061] In some embodiments, the ratio of the volume of the first solvent to the mass of 4-methyl-1,3-cyclohexane diamine and di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is (2-10) mL:1 g.

[0062] When the proportion of the first solvent is less than 2, the solubility of the reaction raw materials is reduced, the probability of collision between the raw materials is reduced, and the reaction speed is reduced; when the proportion of the first solvent is greater than 10, the concentration of the reaction raw materials is too low, which also leads to a reduction in the reaction speed, and solvent is wasted. Therefore, in the embodiments of the present application, the ratio of the volume of the first solvent to the mass sum of 4-methyl-1,3-cyclohexane diamine and (4-bromo-2-substituted butane-1,1-diyl) di-t-butyl dicarbamate is in the range of (2-10):1 (mL / g), which is more appropriate.

[0063] In some preferred embodiments, the ratio of the volume of the first solvent to the mass sum of 4-methyl-1,3-cyclohexane diamine and (4-bromo-2-substituted butane-1,1-diyl) di-t-butyl dicarbamate is (2-8) mL:1 g.

[0064] In some embodiments, the molar ratio of the catalyst to the 4-methyl-1,3-cyclohexane diamine is (1.3-5):1.

[0065] In the embodiments of the present application, the main role of the catalyst is to remove the hydrogen atom of the 4-methyl-1,3-cyclohexane diamine, so as to facilitate the attack of the nucleophile. When the proportion of the catalyst is less than 1.3, the hydrogen removal efficiency is low; when the proportion of the catalyst is greater than 5, the basicity of the solution is too strong, which will interfere with the nucleophilic substitution reaction, and the catalyst is wasted.

[0066] In some preferred embodiments, the molar ratio of the catalyst to the 4-methyl-1,3-cyclohexane diamine is (2-4):1.

[0067] In some embodiments, the step of deprotecting the above-mentioned (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl)) tetra-t-butyl ester tetraaminoformate to obtain the methylcyclohexane diamine derivative shown in Formula I specifically comprises:

[0068] After the first solvent in the system after the spin-drying nucleophilic substitution reaction, the second solvent and the deprotection agent are added to the (((4-methylcyclohexane-1,3-diyl)bis(azanediyl))bis(2-substituted butane-4,1,1-triyl)) tetra-t-butyl ester tetraaminoformate, and after reaction at 30-80°C for 1-3 h, the deprotection neutralizing agent is added and the organic phase is dried, to obtain the methylcyclohexane diamine derivative shown in Formula I.

[0069] In some embodiments, the volume of the second solvent is 20-150% of the volume of the first solvent.

[0070] The second solvent is used as a solvent for the deprotection reaction, and too little amount of the second solvent cannot dissolve the raw material, resulting in a low yield; too much amount of the second solvent makes the concentration of the deprotection agent in the reaction system too low, and the deprotection reaction speed is reduced, and the solvent is wasted.

[0071] In some preferred embodiments, the volume amount of the second solvent is 80% to 120% of the volume amount of the first solvent.

[0072] In some embodiments, the first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, 1,2-dichloroethane, and the second solvent is selected from dichloromethane or chloroform.

[0073] The catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate.

[0074] In some preferred embodiments, the first solvent is xylene or solvent oil, the second solvent is dichloromethane, and the catalyst is potassium carbonate.

[0075] In some embodiments, the deprotection agent is trifluoroacetic acid or dilute hydrochloric acid, and the deprotection neutralizing agent is selected from one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide.

[0076] In some preferred embodiments, the deprotection agent is trifluoroacetic acid, and the deprotection neutralizing agent is sodium bicarbonate.

[0077] The application provides an application of the methylcyclohexanediamine derivative or the methylcyclohexanediamine derivative prepared by the above preparation method in curing of an epoxy resin.

[0078] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments of the application, which are only used to illustrate but not limit the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the application.

[0079] Embodiment 1

[0080] A preparation method of a methylcyclohexanediamine derivative includes the following steps:

[0081] A reactor was charged with toluene (160 mL), 4-methyl-1,3-cyclohexane diamine (6.25 g, 0.05 mol), di-tert-butyl (4-bromo-2-methylbutane-1,1 - diyl)diaminocarboxylate (38.01 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) and heated to 70 °C for 12 h. The reaction progress was followed by TLC. After the reaction was completed, the toluene was distilled off and dichloromethane (160 mL) and 10% (v / v) trifluoroacetic acid were added and heated to 60 °C for 1 h. The reaction was neutralized by adding 100 mL of saturated aqueous sodium bicarbonate solution. The organic phase was dried over anhydrous sodium sulfate and the organic phase was distilled off and finally dried under vacuum at 80 °C to give Yield 97.2%.

[0082] The above reaction scheme is:

[0083]

[0084] Example 2

[0085] A methylcyclohexanediamine derivative was prepared by the following steps:

[0086] A reactor was charged with toluene (160 mL), 4-methyl-1,3-cyclohexane diamine (6.25 g, 0.05 mol), di-tert-butyl (4-bromo-2-methylbutane-1,1 - diyl)diaminocarboxylate (38.01 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) and heated to 70 °C for 12 h. The reaction progress was followed by TLC. After the reaction was completed, the toluene was distilled off and dichloromethane (160 mL) and 10% (v / v) trifluoroacetic acid were added and heated to 60 °C for 1 h. The reaction was neutralized by adding 100 mL of saturated aqueous sodium bicarbonate solution. The organic phase was dried over anhydrous sodium sulfate and the organic phase was distilled off and finally dried under vacuum at 80 °C to give

[0087] Yield 97.2%.

[0088] The above reaction scheme is:

[0089]

[0090] Example 3

[0091] A methylcyclohexanediamine derivative was prepared by the following steps:

[0092] In a reactor, acetonitrile (160 mL), 4-methyl-1,3-cyclohexane diamine (6.25 g, 0.05 mol), di-tert-butyl (4-bromo-2-ethylbutane-1,1-diyl)dicarbamate (39.41 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) were added successively, and the reaction was carried out at 80 °C for 9 h. The reaction progress was tracked by TLC. After the reaction was completed, the acetonitrile was evaporated, dichloromethane (180 mL) and 10% (v / v) dilute hydrochloric acid were added, and the reaction was carried out at 70 °C for 2 h. Then 100 mL of saturated sodium bicarbonate aqueous solution was added to neutralize the dilute hydrochloric acid, the liquid was separated, the organic phase was dried over anhydrous sodium sulfate, the organic phase was evaporated, and finally vacuum drying at 70 °C was carried out to obtain Yield 99.2%.

[0093] The above reaction route is:

[0094]

[0095] Example 4

[0096] A methylcyclohexanediamine derivative was prepared by the following steps:

[0097] In a reactor, acetonitrile (160 mL), 4-methyl-1,3-cyclohexane diamine (6.25 g, 0.05 mol), di-tert-butyl (4-bromo-2-ethylbutane-1,1-diyl)dicarbamate (39.41 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) were added successively, and the reaction was carried out at 80 °C for 9 h. The reaction progress was tracked by TLC. After the reaction was completed, the acetonitrile was evaporated, dichloromethane (180 mL) and 10% (v / v) dilute hydrochloric acid were added, and the reaction was carried out at 70 °C for 2 h. Then 100 mL of saturated sodium bicarbonate aqueous solution was added to neutralize the dilute hydrochloric acid, the liquid was separated, the organic phase was dried over anhydrous sodium sulfate, the organic phase was evaporated, and finally vacuum drying at 70 °C was carried out to obtain Yield 92.2%.

[0098] The above reaction route is:

[0099]

[0100] Example 5

[0101] A methylcyclohexanediamine derivative was prepared by the following steps:

[0102] To a reactor was added solvent oil (160 mL), 4-methyl-1,3-cyclohexane diamine (6.25 g, 0.05 mol), 4-bromo-2-(2,2,10,10-tetramethyl-4,8-dioxo-3,9-dioxa-5,7-diazoundec-6-yl)butyric acid methyl ester (42.41 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) sequentially, and the reaction was carried out at 90 °C for 10 h. The reaction progress was tracked by TLC. After the reaction was completed, the solvent oil was evaporated, chloroform (180 mL) and 10% (v / v) trifluoroacetic acid were added, and the reaction was carried out at 60 °C for 3 h. Then, 45 mL of saturated sodium bicarbonate aqueous solution was added to neutralize the trifluoroacetic acid, the mixture was separated, the organic phase was dried over anhydrous sodium sulfate, the organic phase was evaporated, and finally, vacuum drying was carried out at 80 °C to obtain Yield 89.7%.

[0103] The above reaction route is:

[0104]

[0105] Example 6

[0106] A methylcyclohexanediamine derivative was prepared by the following steps:

[0107] To a reactor was added solvent oil (160 mL), 4-methyl-1,3-cyclohexane diamine (6.25 g, 0.05 mol), 4-bromo-2-(2,2,10,10-tetramethyl-4,8-dioxo-3,9-dioxa-5,7-diazoundec-6-yl)butyric acid methyl ester (42.41 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) sequentially, and the reaction was carried out at 90 °C for 10 h. The reaction progress was tracked by TLC. After the reaction was completed, the solvent oil was evaporated, chloroform (180 mL) and 10% (v / v) trifluoroacetic acid were added, and the reaction was carried out at 60 °C for 3 h. Then, 45 mL of saturated sodium bicarbonate aqueous solution was added to neutralize the trifluoroacetic acid, the mixture was separated, the organic phase was dried over anhydrous sodium sulfate, the organic phase was evaporated, and finally, vacuum drying was carried out at 80 °C to obtain Yield 87.7%.

[0108] The above reaction route is:

[0109]

[0110] Example 7

[0111] A methylcyclohexanediamine derivative was prepared by the following steps:

[0112] In a reactor, tetrahydrofuran (160 mL), 4-methyl-1,3-cyclohexanediamine (6.25 g, 0.05 mol), di-tert-butyl (2-(2-bromoethyl)-3,3-dimethylbutane-1,1-diyl)bis(carbamate) (42.21 g, 0.10 mol) and potassium carbonate (13.82 g, 0.10 mol) were added successively and reacted at 100 °C for 8 h, and the reaction progress was tracked by TLC. After the reaction was completed, the solvent oil was spin-dried, chloroform (180 mL) and 10% (v / v) trifluoroacetic acid were added, and reacted at 80 °C for 3 h. The trifluoroacetic acid was neutralized by adding 100 mL of saturated aqueous sodium carbonate solution, the organic phase was dried with anhydrous sodium sulfate, the organic phase was spin-dried, and finally vacuum dried at 90 °C to obtain Yield 89.7%.

[0113] The above reaction scheme is:

[0114]

[0115] Performance test experiment

[0116] 1. Tensile test and bending test

[0117] The methylcyclohexanediamine derivatives prepared in Examples 1-7 (50 g), methylcyclohexanediamine (50 g), IPDA and bisphenol A resin (150 g) were cured at 80 °C for 2 h, and the tensile test and bending test were performed by differential scanning calorimetry (DSC). The test results are shown in Table 1:

[0118] Table 1

[0119]

[0120]

[0121] 2. Chemical resistance

[0122] The methylcyclohexanediamine derivatives of Examples 1-7 (50 g), methylcyclohexanediamine (50 g), IPDA and bisphenol A resin (150 g) were cured at 80 °C for 2 h, coated onto a 4-inch silicon wafer, and then soft-baked at 120 °C for 3 minutes using a hot plate to obtain a cured film with a thickness of 10-20 μm. The film was then heat-treated in a vacuum oxygen-free oven (MOLZK-32D1, MOLZK).

[0123] Specifically, first, heat treatment was performed at 100 °C for 1 hour, then heat treatment was performed at 150 °C for 1 hour by increasing the temperature over 20 minutes, and finally heat treatment was performed at 200 °C for 1.5 hours by increasing the temperature over 20 minutes, and finally a cured film was obtained.

[0124] The cured film was immersed in acetone, DMSO, phenol, and methylamine, respectively, at room temperature for 10 minutes, and then the changes in the cured film after the immersion were observed.

[0125] The case where no cracks or peeling occurred and the change in film thickness before and after the immersion was 1 μm or less was evaluated as A; the case where no cracks or peeling occurred and the change in film thickness before and after the immersion was more than 1 μm was evaluated as B; and the case where no cracks occurred but the swelled cured film was peeled from the substrate was evaluated as C. The test results are shown in Table 2.

[0126] Table 2

[0127]

[0128]

[0129] As seen from the results in Tables 1 and 2, the resin composition formed by mixing the methylcyclohexanediamine derivative prepared in the Examples of the present application with the bisphenol A resin has excellent mechanical properties and excellent chemical resistance.

[0130] It should be understood that the application is not limited to the examples described above, and that all modifications and variations that can be made by a person of ordinary skill in the art based on the above description are intended to be within the scope of the appended claims.

Claims

1. A methylcyclohexanediamine derivative, characterized by, The structural formula of the methylcyclohexanediamine derivative is shown as formula I: Formula I; R1 is selected from one of hydrogen, methyl, ethyl, n-propyl and isopropyl.

2. A process for the preparation of the methylcyclohexanediamine derivative according to claim 1, characterized in that, The preparation method comprises the following steps: The 4-methyl-1,3-cyclohexanediamine shown as formula II and the di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate shown as formula III are subjected to nucleophilic substitution reaction to obtain the ((4-methylcyclohexane-1,3-diyl) bis(azanediyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate tetra-tert-butyl shown as formula IV; wherein R1 in formula III is selected from one of hydrogen, methyl, ethyl, n-propyl and isopropyl; The ((4-methylcyclohexane-1,3-diyl) bis(azanediyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate tetra-tert-butyl shown as formula IV is subjected to deprotection treatment to obtain the methylcyclohexanediamine derivative shown as formula I; The above reaction route is shown as follows: 。 3. The process for the preparation of methylcyclohexanediamine derivatives according to claim 2, characterized in that, The 4-methyl-1,3-cyclohexanediamine shown as formula II and the di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate shown as formula III are subjected to nucleophilic substitution reaction to obtain the ((4-methylcyclohexane-1,3-diyl) bis(azanediyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate tetra-tert-butyl shown as formula IV; wherein R1 in formula III is selected from one of hydrogen, methyl, ethyl, n-propyl and isopropyl; The 4-methyl-1,3-cyclohexanediamine shown as formula II, the di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate shown as formula III, the first solvent and the catalyst are mixed, and nucleophilic substitution reaction is carried out at 60-120 DEG C for 2-12 h to obtain the ((4-methylcyclohexane-1,3-diyl) bis(azanediyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate tetra-tert-butyl shown as formula IV.

4. The process for preparing methylcyclohexanediamine derivatives according to claim 2, characterized in that, The equivalent ratio of the 4-methyl-1,3-cyclohexanediamine and the di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is 1: (2-4).

5. The process for the preparation of methylcyclohexanediamine derivatives according to claim 3, characterized in that, The ratio of the volume of the first solvent to the mass of the 4-methyl-1,3-cyclohexanediamine and the di-tert-butyl (4-bromo-2-substituted butane-1,1-diyl) diaminoformate is (2-10) mL:1 g.

6. The process for the preparation of methylcyclohexanediamine derivatives according to claim 3, characterized in that, The molar ratio of the catalyst to the 4-methyl-1,3-cyclohexanediamine is (1.3-5):

1.

7. The process for preparing methylcyclohexanediamine derivatives according to claim 3, characterized in that, The ((4-methylcyclohexane-1,3-diyl) bis(azanediyl)) bis(2-substituted butane-4,1,1-triyl)) tetraaminoformate tetra-tert-butyl is subjected to deprotection treatment to obtain the methylcyclohexanediamine derivative shown as formula I. The first solvent in the system after spin-drying nucleophilic substitution reaction, a second solvent and a deprotection agent are added to the (((4-methylcyclohexane-1,3-diyl)bis(azadiyl))bis(2-substituted butane-4,1,1-triyl))tetra tert-butyl ester, after reaction at 30-80℃ for 1-3 h, a deprotection neutralizing agent is added and the organic phase is dried to obtain a methylcyclohexane diamine derivative as shown in Formula I.

8. The process for the preparation of methylcyclohexanediamine derivatives according to claim 7, characterized in that, The volume of the second solvent is 20-150% of the volume of the first solvent; The first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, 1,2-dichloroethane, and the second solvent is selected from dichloromethane or chloroform; The catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate.

9. The process for preparing methylcyclohexanediamine derivatives according to claim 7, characterized in that, The deprotection agent is trifluoroacetic acid or dilute hydrochloric acid, and the deprotection neutralizing agent is selected from one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide.

10. Use of the methylcyclohexane diamine derivative of claim 1 in the curing of epoxy resins.

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