Highly active alicyclic amines, processes for their preparation and use

Abstract

The present application provides a kind of high activity alicyclic amine and its preparation method and use.High activity alicyclic amine, include as follows formula 1 shown structure Compound and / or formula 2 shown structure Compound:in formula 1, each R is independently selected from C2-C12 fatty chain segment, preferably C2~C5 fatty chain segment;R1 is formula 2, each R is independently selected from C2-C12 fatty chain segment, preferably C2~C5 fatty chain segment;R2 is the high activity alicyclic amine can be used as auxiliary in green environmental protection water-based polymer material, composite material and other engineering material field, or as epoxy resin composition curing agent is applied to water-based paint field.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a highly active alicyclic amine, its preparation method, and its uses. Background Technology

[0002] With the continuous improvement of living standards and environmental awareness, people's attention to air quality issues continues to rise, and the control of volatile organic compound (VOC) pollution from chemical raw materials is becoming increasingly stringent. The government strictly controls VOCs, promoting the transformation of various industries towards environmentally friendly, low-emission coating processes. In the coatings industry, it has been explicitly stated that water-based coatings should be promoted to reduce atmospheric VOC pollution. Water-based coatings refer to coatings that use water as a dispersion medium. Compared to oil-based coatings that use organic solvents such as toluene, xylene, and benzyl alcohol as dispersion media, their VOC pollution is almost zero. Therefore, the water-based transformation of chemical raw materials is an effective means of reducing VOCs and is one of the important directions for industry development.

[0003] VOC pollution from indoor floor coatings is closely related to every household. CN111363448A discloses an epoxy composition with low VOC, antistatic, and matte finish characteristics, but it uses a polyetheramine-type curing agent, resulting in low curing activity, slow surface drying speed, significantly reducing construction efficiency, and causing severe sagging. CN112175487A discloses an epoxy topcoat curing agent that, while possessing anti-whitening properties, uses a fatty amine curing agent, resulting in low surface hardness and poor compressive and abrasion resistance after curing.

[0004] To address the aforementioned issues, the industry urgently needs to develop a new type of water-based environmentally friendly coating that features fast curing speed, high hardness, and good anti-sagging properties. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, one objective of this invention is to provide a novel highly active alicyclic amine and its preparation method. By introducing an aliphatic amine structure into the hydrophobic and oily 4,4'-diaminodicyclohexylmethane molecule, a novel alicyclic amine with excellent water solubility is obtained, which can be used as an epoxy resin curing agent.

[0006] The novel highly reactive cycloaliphatic amine described in this invention has low steric hindrance in its NH bond participation in chemical reactions and high reactivity. When used as an epoxy resin curing agent, it exhibits excellent curing activity, significantly increasing the degree of curing and thus improving the hardness of the cured product.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a highly active alicyclic amine comprising compounds with the structure shown in Formula 1 and / or compounds with the structure shown in Formula 2:

[0009]

[0010] In Formula 1, R is independently selected from fatty acid chain segments of C2-C12, preferably fatty acid chain segments of C2-C5; R1 is

[0011]

[0012] In Formula 2, R is independently selected from fatty acid chain segments of C2-C12, preferably fatty acid chain segments of C2-C5; R2 is

[0013] Secondly, the present invention provides a method for preparing the above-mentioned highly active alicyclic amine, comprising the following steps:

[0014] S1. First stage reaction: 4,4'-diaminodicyclohexylmethane is mixed with terminal aminoalkylyne and / or terminal cyanoalkylyne, and hydrogen gas is introduced to carry out the first stage reaction;

[0015] S2. Second stage reaction: Add terminal aminoalkylalkyne and / or terminal cyanoalkylalkyne to the reaction system of step S1, and pass hydrogen gas to carry out the second stage reaction to obtain a highly active alicyclic amine.

[0016] In one embodiment, the preparation method involves the following reaction:

[0017]

[0018] In another embodiment, the preparation method involves the following reaction:

[0019]

[0020] In this invention, the terminal aminoalkylyne mentioned in steps S1 and S2 is a C2-C12 terminal aminoalkylyne, such as C2, C4, C6, C8, C10, or C12, preferably at least one of 3-aminopropyne and 4-aminobutyne.

[0021] The terminal cyanoalkylyne is a C2-C12 terminal cyanoalkylyne, such as C2, C4, C6, C8, C10, or C12, preferably at least one of propynenitrile and 4-cyanobutyne;

[0022] Preferably, the terminal aminoalkylyne and / or terminal cyanoalkylyne mentioned in steps S1 and S2 are fed continuously, preferably by dripping, for a feeding time of 5-10 min, for example, 5, 6, 7, 8, 9, or 10 min.

[0023] Preferably, the terminal aminoalkylyne and / or terminal cyanoalkylyne in step S2 uses the same raw materials as in step S1.

[0024] In this invention, the molar ratio of 4,4'-diaminodicyclohexylmethane to the sum of terminal aminoalkylyne and terminal cyanoalkylyne in step S1 is 1:(0.8-2.2), for example 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, preferably 1:(0.9-2.0);

[0025] In step S2, the molar ratio of 4,4'-diaminodicyclohexylmethane to terminal aminoalkylyne or terminal cyanoalkylyne, based on the 4,4'-diaminodicyclohexylmethane described in step S1, is 1:(0.8 to 2.2), for example 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, preferably 1:(0.9 to 2.0).

[0026] In this invention, the reactions described in steps S1 and S2 are both carried out under the action of a hydrogenation catalyst;

[0027] Preferably, the hydrogenation catalyst is selected from at least one of Raney type catalyst, supported nickel catalyst, and cobalt type catalyst, with supported nickel type catalyst being preferred. Existing products can be used, and all are conventional choices in the field. The present invention does not have any special requirements.

[0028] Preferably, the amount of hydrogenation catalyst used in steps S1 and S2 is 1.1-1.3 wt% of the total mass of the system, for example, 1.1, 1.2, or 1.3 wt%.

[0029] In this invention, the hydrogen gas introduction pressure in steps S1 and S2 is 0.1-0.3 MPaA, for example 0.1, 0.2, or 0.3 MPaA.

[0030] In this invention, the reactions described in steps S1 and S2 are carried out at a temperature of 90-110℃, for example, 90, 95, 100, 105, or 110℃, and for a reaction time of 1-4 hours, for example, 1, 2, 3, or 4 hours.

[0031] In this invention, after the reactions described in steps S1 and S2 are completed, post-processing procedures such as distillation to remove residual monomers are also included. These are routine operations in the field, and this invention does not have any special requirements for them.

[0032] Thirdly, the present invention also provides the use of the above-mentioned highly active alicyclic amine, which can be used as an additive in environmentally friendly water-based system products in the field of engineering materials, preferably as an additive in water-based system products of polymer materials and composite materials; or as a curing agent for epoxy resin compositions in the field of water-based coatings, which has the advantages of fast surface drying speed, high hardness, improved construction efficiency, reduced construction costs, and effective improvement of anti-sagging performance, which is in line with industry development trends and has broad market prospects.

[0033] 4,4'-Diaminodicyclohexylmethane is inherently insoluble in water. The aforementioned structural modification imparts water solubility, expanding its application in various industrial and agricultural production fields, such as water-based coatings. This aligns with the industry's development trend towards water-based and environmentally friendly chemical raw materials. Furthermore, the active NH group of 4,4'-diaminodicyclohexylmethane is attached to an alicyclic ring, resulting in significant steric hindrance in chemical reactions. The aforementioned structural modification adds an NH group to the alicyclic chain, giving it the performance advantages of both alicyclic amines and aliphatic amines (such as the excellent segmental rigidity of alicyclic amines). Moreover, the preparation process is simple, low-cost, highly efficient, and utilizes widely available raw materials, making industrialization easy.

[0034] Fourthly, the present invention provides an aqueous epoxy resin composition comprising the above-mentioned highly active cycloaliphatic amine, wherein the composition is prepared from two components, A and B.

[0035] Component A, based on a total mass of 100%, comprises:

[0036]

[0037] Component B, based on 100% of the total mass, comprises:

[0038]

[0039] The mass ratio of component A to component B is 1:(2-3).

[0040] In this invention, the auxiliary agent in component A is selected from BYK-333 from BYK Chemical, and the auxiliary agent in component B is selected from silane coupling agent KH-560;

[0041] The epoxy resin in component B is selected from waterborne epoxy resin emulsions, preferably waterborne epoxy resin emulsions. 0901;

[0042] The filler in component B is selected from at least one of talc and barium sulfate;

[0043] The pigment in component B is selected from at least one of titanium dioxide and iron oxide red.

[0044] The waterborne epoxy resin composition of the present invention can be prepared by conventional physical blending methods. For example, raw materials are weighed and mixed according to the formula to obtain components A and B, and then components A and B are mixed evenly according to the mass ratio to obtain the waterborne epoxy resin composition.

[0045] Fifthly, the present invention provides the use of the above-described waterborne epoxy resin composition in waterborne coating formulations.

[0046] When the above-mentioned waterborne epoxy resin composition is applied to waterborne coatings, it can effectively improve the anti-sagging performance. The maximum non-sagging coating thickness after the paint film is surface dry reaches more than 275μm, which meets the industry requirements.

[0047] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0048] (1) This invention adds aliphatic amine segments to 4,4'-diaminodicyclohexylmethane by structural modification, and invented a new molecule that has both alicyclic amine and aliphatic amine structures. It has excellent comprehensive performance, and the preparation process is simple, low cost, high production efficiency, and has a wide range of raw material sources, making it easy to industrialize.

[0049] (2) When 4,4'-diaminodicyclohexylmethane is used as a curing agent component in epoxy resin compositions, its curing activity is relatively low. After structural modification according to the present invention, the curing activity of the novel alicyclic amine is greatly improved, thereby achieving a higher degree of curing and significantly increasing the hardness of the cured composition.

[0050] (3) 4,4'-Diaminodicyclohexylmethane itself is insoluble in water. After structural modification by the present invention, the novel alicyclic amine has excellent water solubility, which greatly expands the application of 4,4'-diaminodicyclohexylmethane in many industrial and agricultural production fields such as water-based coatings, which helps to protect people's health and promote the development of environmental protection.

[0051] (4) When the waterborne epoxy resin composition of the present invention, which uses alicyclic amine as curing agent, is applied to waterborne environmentally friendly coatings, the surface dries quickly, the hardness after curing is high, the construction efficiency is improved, and the construction cost is reduced; moreover, it gives the coating formulation unique anti-sagging properties, which is in line with the industry development trend and has broad market development prospects.

[0052] (5) 4,4'-Diaminodicyclohexylmethane easily crystallizes into an oily solid at room temperature and requires heating to above 80°C to melt before use, which is very inconvenient for customers. After structural modification according to the present invention, the novel alicyclic amine is a clear and transparent liquid at room temperature, which greatly facilitates the use of downstream customers and is a new product with great competitiveness and market potential. Attached Figure Description

[0053] Figure 1 The left cup contains 4,4'-diaminodicyclohexylmethane (HMDA), an oily hydrophobic amine, which is insoluble in water and appears as a white, oily substance. The right cup contains 1# (a new molecular amine), a highly active alicyclic amine prepared according to Example 1 of this invention, which is completely dissolved in water. Detailed Implementation

[0054] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0055] The main raw materials used in the embodiments and comparative examples of this invention are as follows. Unless otherwise specified, other raw materials and reagents were obtained through commercially available channels:

[0056] 3-Aminopropyne: 99%, Tianmen Hengchang Chemical Co., Ltd.;

[0057] 4-Aminobutyne: 99%, Hubei Guangao Biotechnology Co., Ltd.;

[0058] Propylonitrile: 99%, Runze Local Reagent Co., Ltd.;

[0059] 4,4'-Diaminodicyclohexylmethane: Wanhua Chemical;

[0060] Supported nickel catalyst: SNCAT-2605TE, Shanghai Xunkai New Material Technology Co., Ltd.;

[0061] Polyetheramine: 8100, Wanhua Chemical;

[0062] KH-560: Shandong Yuanjin New Materials Co., Ltd.;

[0063] BYK-333: BYK Chemicals (Tongling) Co., Ltd.;

[0064] Waterborne epoxy resin: 0901, Wanhua Chemical;

[0065] m-Phenylenediamine: 99%, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0066] The performance testing methods used in the various embodiments and comparative examples of this invention are as follows:

[0067] Surface drying time: Refer to GB 1728-1979 Determination of drying time of paint film and putty film;

[0068] Hardness: Refer to GB / T 2411-1980 Shore Hardness Test Method for Plastics, HTS-800D, Shanghai Yizong Precision Instrument Co., Ltd.;

[0069] Paint sagging performance test: Refer to "GB / T 9264-2012 Evaluation of anti-sagging properties of paints and varnishes", BGD225, Biaogeda Precision Instruments Co., Ltd.

[0070] Example 1

[0071] Highly reactive alicyclic amine 1# was prepared according to the following method:

[0072] S1 was prepared under a hydrogen atmosphere of 0.2 MPaA, with the reaction temperature controlled at 100 °C. 3-Aminopropyne (1.9 mol) was added dropwise to a mixture of 4,4'-diaminodicyclohexylmethane (1 mol) and SNCAT-2605TE catalyst (1.2 wt% of the total mass of the reaction system) over a period of 5 min. After the addition was completed, the reaction was maintained at this temperature for 2.5 h. The residual monomer was removed by distillation (96 °C, 2 kPa absolute pressure).

[0073] In step S2, SNCAT-2605TE catalyst (containing 1.2 wt% of the total mass of the reaction system) is added to the system in step S1. Then, under a hydrogen atmosphere of 0.2 MPaA, the reaction temperature is controlled at 100 °C, and 3-aminopropyne (1.9 mol) is added dropwise over a period of 5 min. After the addition is complete, the reaction is maintained at this temperature for 2.5 h. The residual monomer is removed by distillation (96 °C, absolute pressure 2 kPa) to obtain the target product, highly active alicyclic amine 1#.

[0074] The results of the carbon NMR characterization are as follows:

[0075]

[0076] 13 C NMR (CDCl3, 600MHz, TMS): δ24.1(2C), 29.1(2C), 28.3(2C), 31.5(2C), 32.3(2C), 3 2.4(2C), 32.7(2C), 39.1(2C), 43.8(2C), 43.1(1C), 45.2(2C), 46.5(2C), 54.9(2C)

[0077]

[0078] 13 C NMR (CDCl3, 600MHz, TMS): δ24.6(1C), 27.8(2C), 28.3(2C), 31.9(1C), 32.4(2C), 32.7(2 C), 33.4(2C), 39.4(1C), 43.0(1C), 43.1(1C), 46.0(1C), 46.3(1C), 50.3(1C), 54.9(1C)

[0079] Under laboratory conditions (temperature 16℃, humidity 28%), 10g of 4,4'-diaminodicyclohexylmethane and 10g of highly reactive cycloaliphatic amine 1# were dissolved in 100g of water respectively. The solubility of both in water is shown in the figure. Figure 1 (The new molecular amine in the figure is the novel alicyclic amine 1#.)

[0080] Example 2

[0081] Highly reactive alicyclic amine 2# was prepared according to the following method:

[0082] S1 was prepared under a hydrogen atmosphere of 0.1 MPa A, with the reaction temperature controlled at 90 °C. 4-Aminobutyne (0.8 mol) was added dropwise to a mixture of 4,4'-diaminodicyclohexylmethane (1 mol) and SNCAT-2605TE catalyst (1.1 wt% of the total mass of the reaction system) over a period of 8 min. After the addition was completed, the reaction was maintained at this temperature for 12.5 h. The residual monomer was removed by distillation (96 °C, absolute pressure 2 kPa A).

[0083] In step S2, SNCAT-2605TE catalyst (containing 1.1 wt% of the total mass of the reaction system) is added to the system in step S1. Then, under a hydrogen atmosphere of 0.1 MPaA, the reaction temperature is controlled at 90°C, and 4-aminobutyne (0.8 mol) is added dropwise over 8 min. After the addition is complete, the reaction is maintained at this temperature for 1 h. The residual monomer is removed by distillation (96°C, absolute pressure 2 kPa) to obtain the target product, a novel highly active alicyclic amine 2#.

[0084] The results of the carbon NMR characterization are as follows:

[0085]

[0086] 13 C NMR (CDCl3, 600MHz, TMS): δ25.1(2C), 25.5(2C), 25.8(2C), 25.9(2C), 27.1(4C), 3 1.1(4C), 32.3(2C), 41.2(2C), 43.2(1C), 47.1(2C), 49.6(2C), 55.4(2C), 48.6(2C)

[0087]

[0088] 13 C NMR (CDCl3, 600MHz, TMS): δ25.2(1C), 25.4(1C), 25.5(1C), 26.1(1C), 27.8(2C), 28.3(1C), 29.3(1C), 3 2.0(1C), 32.5(2C), 32.4(1C), 33.4(2C), 41.7(1C), 43.1(1C), 47.4(1C), 49.4(2C), 50.3(1C), 54.9(1C)

[0089] Example 3

[0090] The highly active alicyclic amine 3# was prepared according to the following method:

[0091] S1 was prepared under a hydrogen atmosphere of 0.3 MPaA, with the reaction temperature controlled at 110 °C. Propylene nitrile (2.2 mol) was added dropwise to a mixture of 4,4'-diaminodicyclohexylmethane (1 mol) and SNCAT-2605TE catalyst (1.3 wt% of the total mass of the reaction system) over a period of 10 min. After the addition was completed, the reaction was maintained at the temperature for 4 h. The residual monomer was removed by distillation (96 °C, 2 kPa absolute pressure).

[0092] In step S2, SNCAT-2605TE catalyst (containing 1.3 wt% of the total mass of the reaction system) is added to the system in step S1. Then, under a hydrogen atmosphere of 0.3 MPaA, the reaction temperature is controlled at 110 °C, and propyne nitrile (2.2 mol) is added dropwise over a period of 10 min. After the addition is complete, the reaction is maintained at this temperature for 4 h. The residual monomer is removed by distillation (96 °C, absolute pressure 2 kPa) to obtain the target product, highly active alicyclic amine 3#, with the same structure as highly active alicyclic amine 1# in Example 1.

[0093] Example 4

[0094] Aqueous epoxy resin compositions were prepared according to the following method:

[0095] Prepare components A and B separately:

[0096] Component A: Mix 45g of highly active cycloaliphatic amine 1#, 19.7g of water, 35g of talc, and 0.3g of additive BYK-333 until homogeneous.

[0097] Component B: Mix 37g epoxy resin, 35g talc, 30g titanium dioxide, and 8g KH-560 evenly.

[0098] Components A and B were mixed evenly at a mass ratio of 1:2.5 (total amount 500g) to obtain an aqueous epoxy resin composition. The performance test results are shown in Table 1.

[0099] Example 5

[0100] Aqueous epoxy resin compositions were prepared according to the following method:

[0101] Prepare components A and B separately:

[0102] Component A: Mix 50g of novel high-activity cycloaliphatic amine 2#, 19.8g of water, 30g of talc, and 0.2g of additive BYK-333 evenly.

[0103] Component B: Mix 25g epoxy resin, 50g barium sulfate, 13g iron oxide red, and 12g KH-560 evenly.

[0104] Components A and B were mixed evenly at a mass ratio of 1:2 (total 500g) to obtain an aqueous epoxy resin composition. The performance test results are shown in Table 1.

[0105] Example 6

[0106] Aqueous epoxy resin compositions were prepared according to the following method:

[0107] Prepare components A and B separately:

[0108] Component A: Mix 40g of novel high-activity cycloaliphatic amine 3#, 25g of water, 34.6g of talc, and 0.4g of additive BYK-333 evenly.

[0109] Component B: Mix 50g epoxy resin, 32g talc, 10g titanium dioxide, and 8g KH-560 evenly.

[0110] Components A and B were mixed evenly at a mass ratio of 1:3 (total amount 500g) to obtain an aqueous epoxy resin composition. The performance test results are shown in Table 1.

[0111] Example 7

[0112] Aqueous epoxy resin compositions were prepared according to the following method:

[0113] Prepare components A and B separately:

[0114] Component A: Mix 50g of novel high-activity cycloaliphatic amine 1#, 15g of water, 34.8g of talc, and 0.2g of additive BYK-333 evenly.

[0115] Component B: Mix 35g epoxy resin, 25g barium sulfate, 30g iron oxide red, and 10g KH-560 evenly.

[0116] Components A and B were mixed evenly at a mass ratio of 1:2 (total 500g) to obtain an aqueous epoxy resin composition. The performance test results are shown in Table 1.

[0117] Comparative Example 1

[0118] Aqueous epoxy resin compositions were prepared using the method described in Example 4, except that polyetheramine was used. D-400 replaces the novel highly active cycloaliphatic amine 1# in component A. The performance test results of this group of epoxy resin compositions are shown in Table 1.

[0119] Comparative Example 2

[0120] Aqueous epoxy resin compositions were prepared using the method of Example 4, except that m-phenylenediamine was used to replace the novel highly active cycloaliphatic amine 1# in component A. The performance test results of this group of epoxy resin compositions are shown in Table 1.

[0121] Comparative Example 3

[0122] Aqueous epoxy resin compositions were prepared using the method of Example 4, except that the novel highly active cycloaliphatic amine 1# in component A was replaced with the product of step S1 of Example 1. The performance test results of this group of epoxy resin compositions are shown in Table 1.

[0123] The surface drying time, hardness, and coating sag properties of the waterborne epoxy resin compositions prepared in Examples 4-7 and Comparative Examples 1-3 were tested, and the test results are shown in Table 1.

[0124] Table 1 Performance test results of epoxy resin compositions

[0125]

[0126] Results analysis:

[0127] Examples 4-7 used the novel highly reactive alicyclic amine prepared according to the present invention to prepare waterborne epoxy resin compositions. Comparative Examples 1-2 used other waterborne amine curing agents to prepare epoxy resin compositions. Comparative Example 3 used the product of step S1 of Example 1 as a curing agent to prepare an epoxy resin composition. As shown in Table 1, compared with Comparative Examples 1-2, the surface drying time of Examples 4-7 was significantly shortened and the surface drying speed was significantly improved. This is because, after amine alkylation of the alicyclic amine 4,4'-diaminodicyclohexylmethane, aliphatic amine segments were introduced, reducing the steric hindrance of NH participating in the epoxy resin curing reaction and increasing the reactivity, thus accelerating the surface drying speed. Simultaneously, with the increase in reactivity, the degree of reaction increased accordingly, and the hardness of the cured product also improved, as shown in Table 1 for Examples 4-7. Compared with Comparative Example 3, the aliphatic amine segments in Examples 4-7 are longer, the steric hindrance of NH participating in the epoxy resin curing reaction is smaller, and the reactivity is higher, resulting in better surface drying time, hardness, and other properties. Furthermore, with the introduction of aliphatic amine segments, the prepared compositions exhibited improved anti-sagging properties, and the maximum coating thickness in Examples 4-7 was significantly higher than that in the three comparative groups.

[0128] In summary, the novel highly active cycloaliphatic amine prepared by this invention is suitable for use in waterborne epoxy resin systems. Epoxy resin compositions prepared using it as a curing agent exhibit fast surface drying speed, high hardness, excellent anti-sagging properties, and superior overall performance.

[0129] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A high activity alicyclic amine characterized in that, A compound comprising a structure represented by Formula 1 and / or a compound comprising a structure represented by Formula 2: Formula 1 Formula 2. In Formula 1, each R is independently selected from a C2-C12 aliphatic segment; R1is In formula 2, each R is independently selected from a C2-C12 aliphatic segment; R2is 2. The high activity alicyclic amine according to claim 1, characterized by In Formula 1, each R is independently selected from a C2-C5 aliphatic segment.

3. The high activity alicyclic amine according to claim 1, wherein In Formula 2, each R is independently selected from a C2-C5 aliphatic segment.

4. A process for the preparation of a high activity alicyclic amine according to any one of claims 1 to 3, characterized in that the step Comprising: S1. performing a first-stage reaction: mixing 4,4'-diaminodicyclohexyl methane with terminal aminoalkynyl and / or terminal cyanoalkynyl, and performing a first-stage reaction by introducing hydrogen gas; S2. performing a second-stage reaction: adding terminal aminoalkynyl and / or terminal cyanoalkynyl to the reaction system of step S1, and performing a second-stage reaction by introducing hydrogen gas to obtain a high-activity alicyclic amine.

5. The preparation method according to claim 4, characterized in that, The terminal aminoalkynyl in step S1 and step S2 is a C2-C12 terminal aminoalkynyl. The terminal cyanoalkynyl is a C2-C12 terminal cyanoalkynyl.

6. The preparation method according to claim 4, characterized in that, The terminal aminoalkynyl is at least one of 3-aminopropynyl and 4-aminobutyryl.

7. The preparation method according to claim 4, characterized in that, The terminal cyanoalkynyl is at least one of propynyl cyanide and 4-cyanobutyryl.

8. The preparation method according to claim 4, characterized in that, The terminal aminoalkynyl and / or terminal cyanoalkynyl in step S1 and step S2 is added continuously, and the feeding time is 5-10 min.

9. The production method according to claim 8, characterized by, The terminal aminoalkynyl and / or terminal cyanoalkynyl is added dropwise.

10. The method of claim 4, wherein, The terminal aminoalkynyl and / or terminal cyanoalkynyl in step S2 is the same raw material as in step S1.

11. The preparation method according to claim 4, characterized in that, The molar ratio of the 4,4'-diaminodicyclohexyl methane to the sum of the terminal aminoalkynyl and terminal cyanoalkynyl in step S1 is 1:(0.8-2.2); and / or In step S2, the molar ratio of the 4,4'-diaminodicyclohexyl methane to the terminal aminoalkynyl or terminal cyanoalkynyl is 1:(0.8-2.2) based on the 4,4'-diaminodicyclohexyl methane in step S1.

12. The method of claim 11, wherein, The molar ratio of the 4,4'-diaminodicyclohexyl methane to the sum of the terminal aminoalkynyl and terminal cyanoalkynyl in step S1 is 1:(0.9-2.0).

13. The method of claim 11, wherein, In step S2, the molar ratio of the 4,4'-diaminodicyclohexyl methane to the terminal aminoalkynyl or terminal cyanoalkynyl is 1:(0.9-2.0) based on the 4,4'-diaminodicyclohexyl methane in step S1.

14. The method of claim 4, wherein, The reactions in step S1 and step S2 are both performed in the presence of a hydrogenation catalyst.

15. The method of claim 14, wherein, The hydrogenation catalyst is at least one selected from Raney catalyst, supported nickel catalyst, and cobalt catalyst.

16. The method of claim 14, wherein, The amount of the hydrogenation catalyst used in step S1 and step S2 is 1.1-1.3 wt% based on the total mass of the system.

17. The preparation method according to claim 4, characterized in that, The hydrogen gas is introduced at a pressure of 0.1-0.3 MPa.

18. The method of claim 4, wherein, The reaction temperature in step S1 and step S2 is 90-110°C, and the reaction time is 1-4 h.

19. Use of the high-activity alicyclic amine of any one of claims 1-3 or the high-activity alicyclic amine prepared by the method of any one of claims 4-18 as an additive in an environmentally friendly water-based system product in the field of engineering materials.

20. The use according to claim 19, characterized in that, Use as an additive in a water-based system product of a high polymer material or a composite material.

21. Use of the high-activity alicyclic amine of any one of claims 1-3 or the high-activity alicyclic amine prepared by the method of any one of claims 4-18 as a curing agent for an epoxy resin composition in the field of water-based paints.

22. An aqueous epoxy resin composition, characterized by The composition comprises the high-activity alicyclic amine according to any one of claims 1-3 or is prepared from the A, B two-component system according to any one of claims 4-18 The high-activity alicyclic amine is prepared by the method, and the composition is prepared from the A, B two-component system; The A component comprises, based on the total mass of 100%: The B component comprises, based on the total mass of 100%: The mass ratio of the A component to the B component is 1:(2-3).

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