CN115947661A - Cyclohexylamine derivative, preparation and application thereof - Google Patents
Cyclohexylamine derivative, preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a cyclohexylamine derivative and a preparation method and application thereof. The addition condition of the aliphatic diamine and the acrylonitrile is controllable, and the chain length of the cyclohexylamine derivative can be regulated and controlled by the number of aliphatic diamine carbons. The cyclohexylamine derivative has good water solubility, high curing speed, high hardness of cured products and good thermal-oxidative aging resistance, the method is simple to operate, the reaction condition is controllable, the yield is high, and the product is beneficial to industrial production; the organic amine can be used as an auxiliary agent to be applied to the fields of engineering materials such as high polymer materials, composite materials and the like, and is suitable for high-grade environment-friendly seam beautifying agents, seam wang, water-based epoxy colored sand and water permeable bricks.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a cyclohexylamine derivative, and preparation and application thereof.
Background
Amine curing agents are organic polyamines which are widely used as curing agents for epoxy resins. There are four classes of single polyamines, mixed polyamines, modified polyamines and eutectic mixed polyamines. Amine curing agents for curing epoxy coatings at normal temperature can be classified into reactive curing agents and catalytic curing agents. Among them, the reactive curing agents generally used for curing epoxy coatings at normal temperature include:
1. aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyethylenepolyamine, etc. The aliphatic amine curing agent has the characteristics that (1) the activity is high, and the aliphatic amine curing agent can be cured at room temperature; (2) the reaction is violent in heat release and short in working life; (3) Generally, post-curing is needed, the curing is carried out for about 7 days at room temperature, and the post-curing is carried out for 2 h/80-100 ℃, so that the performance is better; (4) The thermal deformation temperature of the condensate is lower, generally 80-90 ℃; (5) the cured product has high brittleness; and (6) the volatility and the toxicity are high. Therefore, they are not generally used as a curing agent for coating materials directly, but are modified by introducing a new molecular structure through addition or condensation reaction.
2. Alicyclic polyamine, alicyclic amine is amine compound containing alicyclic ring (cyclohexyl, hetero-oxygen, ammonia atom six-membered ring) in molecular structure. Most of the liquid is low-viscosity liquid, the pot life is longer than that of fatty amine, and the chroma and the luster of a cured product are superior to those of the fatty amine and polyamide; medium-temperature curing, high price, good transparency, good weather resistance and high mechanical strength of a cured product; the modified product can be cured at room temperature. The most common is isophorone diamine (cycloaliphatic amine). However, they are not generally used as curing agents for coating materials directly but are modified by introducing a new molecular structure through addition or condensation reaction.
HMDA (4,4' -diamino-dicyclohexylmethane) is an important alicyclic amine organic intermediate, and is mainly used as a curing agent and a raw material of HMDI (dicyclohexylmethane diisocyanate). Compared with the traditional aromatic diamine compound, the HMDA has an alicyclic structure and has no pi electrons in the molecular structure, so that the HMDA has excellent special performance. Such as good oxidation resistance, low dielectric constant, good solubility, low refractive index, low optical loss, good flexibility, etc. The method has wide application prospect and high popularization value in high and new technology fields such as optical materials, water-based materials, liquid crystal display materials, optical fiber communication materials and the like. HMDI is prepared after HMDA phosgenation, and downstream products of the HMDI are endowed with excellent performances of yellowing resistance, oil resistance, pulverization resistance, outdoor solarization resistance and the like, so that the HMDI becomes a new material with great development prospect. Has received great attention at home and abroad in recent years, and has good market prospect in the fields of high-end automobile coatings, powder coatings, wood paints and the like.
Disclosure of Invention
Aiming at the defects of the existing amine curing agent in properties, the invention combines the excellent performance of the alicyclic structure in HMDA, and on the basis, the invention synthesizes a series of cyclohexylamine derivatives with the alicyclic structure and discloses a preparation method thereof. A cyclohexylamine derivative having the structure:
The cyclohexylamine derivative is obtained by S1 Michael addition reaction, S2 cyano reduction reaction, S3 condensation reaction and S4 imine reduction reaction, and the reaction equation is as follows:
s1: carrying out Michael addition reaction, and reacting aliphatic diamine with acrylonitrile in a solvent medium within a certain temperature range to obtain an intermediate 1;
s2: performing cyano reduction reaction, namely adding a catalyst into the intermediate 1 in a hydrogen environment, heating to a certain temperature, and reacting to obtain an intermediate 2;
s3: condensation reaction, namely reacting the intermediate 2 with cyclohexanone under the catalysis of a catalyst to obtain an intermediate 3;
s4: and (3) carrying out imine reduction reaction, adding a catalyst into the intermediate 3 in a hydrogen environment, heating to a certain temperature, and reacting to obtain the cyclohexylamine derivative.
The solvent in S1 is one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, tert-butanol and ethylene glycol, preferably methanol; the molar ratio of the aliphatic diamine to the acrylonitrile is 1:2; the reaction temperature range is 5-10 ℃.
The hydrogen environment in the S2 is 1.5-2.2MPa; the reaction temperature is 65-70 ℃; the catalyst is Pd/C, pt/C, ru/C, rh/C, ni/SiO 2 、Co/SiO 2 、Pd/SiO 2 、Pt/SiO 2 Preferably Ru/C.
The catalyst in S3 is one or more of acetic acid, glycolic acid, p-toluenesulfonic acid and methanesulfonic acid, and is preferably p-toluenesulfonic acid; the molar ratio of intermediate 2 to cyclohexanone was 1:2.
The hydrogen environment in the S4 is 0.3-0.6MPa, preferably 0.5MPa; the catalyst is Raney nickel or Raney cobalt; the reaction temperature is 60-70 ℃.
The organic amine can be used as an auxiliary agent to be applied to a water-based system product of an engineering material, preferably used as an auxiliary agent to be applied to a water-based system product of a high polymer material and a composite material, and is particularly used for an environment-friendly seam beautifying agent, a seam king and a water permeable brick.
The invention has the beneficial effects that:
(1) The addition condition of the aliphatic diamine and the acrylonitrile is controllable, and the chain length of the cyclohexylamine derivative can be regulated and controlled by the number of aliphatic diamine carbons.
(2) 2 cyclohexylamines are introduced into the structure, so that the water solubility is increased, the curing speed is accelerated, the hardness of a cured product is high, and the thermo-oxidative aging resistance is good.
(3) The method has the advantages of simple operation, controllable reaction conditions, high yield, contribution to industrial production of products, high atom utilization rate and accordance with the modern green industrial concept.
Detailed Description
Firstly, the following steps: process for preparing cyclohexylamine derivatives
The preparation method of the compound is explained in detail by combining the specific molecular structure of the cyclohexylamine derivative.
Example 1: when n =2, the compound has the following molecular structure, we name CY-2, and the specific synthetic route is shown below.
Preparation of intermediate 1: under the mechanical stirring, adding ethylenediamine (1 eq) into a three-neck flask, adding methanol (3V), cooling to 5-10 ℃, dropwise adding acrylonitrile (2 eq), controlling the temperature in the dropwise adding process to be not more than 10 ℃, reacting for 1 hour after the dropwise adding is finished, obtaining a methanol solution of an intermediate 1, and directly carrying out the next reaction.
Preparation of intermediate 2: transferring the methanol solution of the intermediate 1 (1 eq) into a high-pressure reaction kettle, adding Ru/C (5% mol), replacing for 3 times by nitrogen and 3 times by hydrogen, maintaining the pressure at 1.5-2.2MPa, heating to 65-70 ℃ and reacting for 1.5 hours, and finishing the reaction. Cooling to room temperature, recovering normal pressure, replacing with nitrogen for 2 times, filtering, recovering Ru/C catalyst to obtain intermediate 2 filtrate, and directly carrying out the next reaction without further purification.
Preparation of intermediate 3: transferring the methanol solution of the intermediate 2 (1 eq) into a normal pressure reaction kettle, adding p-toluenesulfonic acid (5% mol), maintaining the system temperature at 25-30 ℃, dropwise adding cyclohexanone (2 eq), keeping the dropwise adding process at 35 ℃ or below, keeping the temperature for 10 hours after the dropwise adding is finished, and finishing the reaction. The solvent was concentrated to give an oil which was washed sequentially with 5% sodium hydroxide solution and water to give intermediate 3.
Preparation of CY-2: transferring the intermediate 3 (1 eq) to a high-pressure reaction kettle, adding ethanol (3V), adding Raney nickel (5% mol), replacing for 3 times by nitrogen and 3 times by hydrogen, maintaining the pressure at 0.5MPa, heating to 60-70 ℃ and reacting for 3 hours, and finishing the reaction. Cooling to room temperature, recovering normal pressure, replacing with nitrogen for 2 times, filtering, recovering Raney nickel catalyst, vacuum concentrating solvent to obtain crude product, and rectifying to obtain fine CY-2 product.
Example 2: when n =3, the compound has the following molecular structure, we name CY-3, and the specific synthetic route is shown below.
Preparation of intermediate 1: under the mechanical stirring, adding propane diamine (1 eq) into a three-neck flask, adding methanol (3V), cooling to 5-10 ℃, dropwise adding acrylonitrile (2 eq), controlling the temperature in the dropwise adding process to be not more than 10 ℃, reacting for 1 hour after the dropwise adding is finished, obtaining a methanol solution of an intermediate 1, and directly carrying out the next reaction.
Preparation of intermediate 2: transferring the methanol solution of the intermediate 1 (1 eq) into a high-pressure reaction kettle, adding Ru/C (5% mol), replacing for 3 times by nitrogen and 3 times by hydrogen, maintaining the pressure at 1.5-2.2MPa, heating to 65-70 ℃ and reacting for 1.5 hours, and finishing the reaction. And cooling to room temperature, recovering the normal pressure, replacing with nitrogen for 2 times, filtering, recovering the Ru/C catalyst to obtain an intermediate 2 filtrate, and directly carrying out the next reaction without further purification.
Preparation of intermediate 3: transferring the methanol solution of the intermediate 2 (1 eq) into a normal-pressure reaction kettle, adding p-toluenesulfonic acid (5 mol%), maintaining the system temperature at 25-30 ℃, dropwise adding cyclohexanone (2 eq), keeping the dropwise adding process at 35 ℃ or less, keeping the temperature for 10 hours after the dropwise adding is finished, and finishing the reaction. The solvent was concentrated to give an oil which was washed sequentially with 5% sodium hydroxide solution and water to give intermediate 3.
Preparation of CY-3: transferring the intermediate 3 (1 eq) into a high-pressure reaction kettle, adding ethanol (3V), adding Raney nickel (5% mol), replacing for 3 times by nitrogen and replacing for 3 times by hydrogen, maintaining the pressure at 0.5MPa, heating to 60-70 ℃ and reacting for 3 hours, and finishing the reaction. Cooling to room temperature, recovering normal pressure, replacing with nitrogen for 2 times, filtering, recovering Raney nickel catalyst, vacuum concentrating solvent to obtain crude product, and rectifying to obtain CY-3 refined product.
Example 3: when n =4, the compound has the following molecular structure, we name CY-4, and the specific synthetic route is shown below.
Referring to example 1, the specific preparation method can be used, and the raw material ethylenediamine in example 1 is replaced by butanediamine to obtain CY-4.
When n =5, we name CY-5, and the process for its preparation still refers to example 1, simply by replacing ethylenediamine with the corresponding pentanediamine to give CY-5.
When n is other number, the same can be said for the preparation method.
II, secondly, the method comprises the following steps: and (3) performance testing:
surface dry time test: refer to GB 1728-1979 determination of drying time of paint film/putty film;
and (3) viscosity testing: bohler fly viscometer, normal temperature, 20# rotor;
shore hardness: refer to the method for testing Shore hardness of plastics GB/T2411-1980
The specific components are all conventional and commercially available except that the cyclohexylamine derivative to be protected according to the present invention is prepared by the present invention.
Test example 1: preparation of epoxy curing agent: (specific Components of the agent A and the agent B are not distinguished)
Placing 15 parts of cyclohexylamine derivative CY-2, 20 parts of polyetheramine T403, 28 parts of waterborne epoxy resin, 20 parts of n-butyl glycidyl ether and 7 parts of bentonite 6 parts of water in a mixing container, uniformly stirring, and selecting a proper mould to obtain a strip-shaped epoxy resin test sample 1.
Test example 2: preparation of epoxy curing agent: (specific A agent and B agent components are not distinguished)
Placing 15 parts of cyclohexylamine derivative CY-3, 20 parts of polyetheramine T403, 28 parts of waterborne epoxy resin, 20 parts of n-butyl glycidyl ether and 7 parts of bentonite 6 parts of water in a mixing container, uniformly stirring, and selecting a proper mould to obtain a strip-shaped epoxy resin test sample 2.
Test example 3: preparation of epoxy curing agent: (specific A agent and B agent components are not distinguished)
Placing 15 parts of cyclohexylamine derivative CY-5, 20 parts of polyetheramine T403, 28 parts of waterborne epoxy resin, 20 parts of n-butyl glycidyl ether and 7 parts of 6 parts of bentonite water in a mixing container, uniformly stirring, and selecting a proper mold to obtain a strip-shaped epoxy resin test sample 3.
Comparative test example 1
An aqueous epoxy resin composition was prepared by the method of test example 1 except that 4,4-diaminodiphenylmethane was used in place of cyclohexylamine derivative CY-2 obtained in example 1 in the components to obtain epoxy resin comparative sample 1.
The performance test results of the epoxy resin composition are shown in table 1.
The water-based epoxy resin compositions prepared in examples 1 to 4 and comparative example 1 were subjected to tack free time, hardness, and epoxy curing viscosity tests, and the results are shown in Table 1
TABLE 1 Performance testing of waterborne epoxy resin compositions
| Test sample | Surface drying time/min | hardness/Shore D | Viscosity/cps of epoxy curing agent |
| Epoxy resin test sample 1 | 41 | 92 | 1810 |
| Epoxy resin test sample 2 | 51 | 91 | 1750 |
| Epoxy resin test sample 3 | 46 | 88 | 1770 |
| Epoxy resin comparative test sample 1 | 132 | 87 | 2200 |
The waterborne epoxy resin curing agent prepared from the cyclohexylamine derivative has the advantages of quick surface drying time and high hardness, can be used as a waterborne curing material, can be used as a curing agent of a crack sealing agent in specific application, is used in the field of building materials, and has excellent performance and excellent effect.
Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (9)
1. A cyclohexylamine derivative having the structure:
2. The cyclohexylamine derivative according to claim 1, which is obtained by S1 Michael addition reaction, S2 cyano reduction reaction, S3 condensation reaction, and S4 imine reduction reaction, and which has the following reaction equation:
s1: carrying out Michael addition reaction, wherein aliphatic diamine reacts with acrylonitrile in a solvent medium to obtain an intermediate 1;
s2: performing cyano reduction reaction, namely adding a catalyst into the intermediate 1 in a hydrogen environment, heating, and reacting to obtain an intermediate 2;
s3: condensation reaction, namely reacting the intermediate 2 with cyclohexanone under the catalysis of a catalyst to obtain an intermediate 3;
s4: and (3) carrying out imine reduction reaction, adding a catalyst into the intermediate 3 in a hydrogen environment, heating, and reacting to obtain the cyclohexylamine derivative.
3. The method for preparing cyclohexylamine derivative according to claim 2, wherein the solvent in S1 is one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, t-butanol, and ethylene glycol; the molar ratio of the aliphatic diamine to the acrylonitrile is 1:2; the reaction temperature range is 5-10 ℃.
4. The method for producing a cyclohexylamine derivative according to claim 2, wherein the hydrogen atmosphere in S2 is 1.5 to 2.2MPa; the reaction temperatureThe temperature is 65-70 ℃; the catalyst is Pd/C, pt/C, ru/C, rh/C, ni/SiO 2 、Co/SiO 2 、Pd/SiO 2 、Pt/SiO 2 One or more of (a).
5. The method for preparing cyclohexylamine derivative according to claim 2, wherein the catalyst in S3 is one or more of acetic acid, glycolic acid, p-toluenesulfonic acid, and methanesulfonic acid; the molar ratio of intermediate 2 to cyclohexanone was 1:2.
6. The method for producing a cyclohexylamine derivative according to claim 2, wherein the hydrogen atmosphere in S4 is 0.3 to 0.6MPa; the catalyst is Raney nickel or Raney cobalt; the reaction temperature is 60-70 ℃.
7. Use of a cyclohexylamine derivative according to any one of claims 1 to 6 as an adjuvant in the production of aqueous systems for engineering materials.
8. The use of the cyclohexylamine derivative according to claim 7, characterized in that the cyclohexylamine derivative is used as an auxiliary agent in the production of aqueous systems of high molecular materials and composite materials.
9. Use of cyclohexylamine derivatives according to claim 7, characterized in that they are used in eco-friendly jointing agents, joint closets, water permeable bricks.
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Citations (2)
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| CN1211989A (en) * | 1996-01-05 | 1999-03-24 | 联邦科学技术研究组织 | Composition and method for delivery of nucleic acids |
| CN101643537A (en) * | 2008-08-06 | 2010-02-10 | 气体产品与化学公司 | Alkylated aminopropylated ethylenediamines and uses thereof |
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- 2022-12-30 CN CN202211723622.8A patent/CN115947661A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211989A (en) * | 1996-01-05 | 1999-03-24 | 联邦科学技术研究组织 | Composition and method for delivery of nucleic acids |
| CN101643537A (en) * | 2008-08-06 | 2010-02-10 | 气体产品与化学公司 | Alkylated aminopropylated ethylenediamines and uses thereof |
Non-Patent Citations (4)
| Title |
|---|
| BURKHARD KLENKE等: "Synthesis and Biological Evaluation of s-Triazine Substituted Polyamines as Potential New Anti-Trypanosomal Drugs", 《JOURNAL OF MEDICINAL CHEMISTRY》, vol. 44, no. 21, pages 3440 - 3452, XP002569599, DOI: 10.1021/JM010854 * |
| HAKKINEN, MERJA R.等: "Synthesis of novel deuterium labelled derivatives of N-alkylated polyamines", 《TETRAHEDRON》, vol. 65, no. 2, pages 547 - 562, XP025716338, DOI: 10.1016/j.tet.2008.10.071 * |
| WEITL, FREDERICK L.等: "Lipophilic enterobactin analogs. Terminally N-alkylated spermine/spermidine catecholcarboxamides", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 46, no. 25, pages 5234 - 5237, XP002222600, DOI: 10.1021/jo00338a042 * |
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