Alkyl aminosilane compounds and methods for their preparation
By designing alicyclic aminosilane compounds with a 4,4-methylene double-bridged structure, the problem of the complex binding process between alicyclic amines and organosilanes was solved, achieving high performance and efficient preparation of the compounds, which are suitable for high-end applications.
Patent Information
- Application Number
- CN202610358626.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-23
- Publication Date
- 2026-05-26
AI Technical Summary
Existing alicyclic amines and organosilanes are difficult to form ideal chemical bonds during the reaction process, resulting in a complex and uncontrollable bonding process. Furthermore, they are difficult to disperse uniformly in the mixed system, which hinders their development in high-end application fields.
A cycloalicyclic aminosilane compound with a 4,4-methylene double-bridged structure was designed. By combining the saturated carbocyclic structure of the dicycloalicyclic amine with a silane group, and using specific reaction conditions and a basic reagent, the reaction was driven to the forward direction, resulting in a product with high yield and purity.
The compound exhibits excellent heat resistance, low volatility, strong interfacial adhesion, and good hydrophobicity. The preparation method is simple and suitable for large-scale industrial production.
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Abstract
Description
Technical Field
[0001] This application relates to the field of fine chemicals, and more specifically, to a dialicyclic aminosilane compound having a 4,4-methylene double-bridged structure and a method for its preparation. Background Technology
[0002] In recent years, with the rapid development of science and technology, people's requirements for the performance of various chemical materials have been increasing, and their application scope has been continuously expanding. In the field of fine chemicals, high-performance chemical materials are crucial for promoting industrial upgrading and technological innovation. Alicyclic amines, due to their unique saturated carbide ring structure and high reactivity, have shown significant application value in several key areas, such as the curing of high-performance polymers (e.g., epoxy resins and polyurethanes), metal corrosion protection, and material surface modification. In the curing of high-performance polymers, cyclocyclic amines can significantly improve the mechanical properties and chemical stability of polymers, enabling their widespread application in high-end fields such as aerospace and automotive manufacturing. In the field of metal corrosion protection, they can form an effective protective film on the metal surface, extending the service life of the metal and reducing resource consumption. In terms of material surface modification, they can endow materials with new properties, such as improving the hydrophilicity or hydrophobicity of the surface, thereby broadening the application scenarios of materials and greatly promoting the development of high-end manufacturing and materials science. However, conventional cyclocyclic amines (such as cyclohexylamine derivatives) often have disadvantages such as high volatility, poor compatibility with substrates, or insufficient weather resistance.
[0003] Organosilane compounds, especially aminosilanes, are renowned for their excellent interfacial bonding ability, hydrophobicity, and thermal stability, and are widely used as coupling agents. Combining them with the saturated carbocyclic structure of alicyclic amines holds promise for developing novel materials that combine excellent heat resistance, low volatility, strong interfacial adhesion, and good hydrophobicity. However, attempts to combine alicyclic amines and organosilanes face numerous challenges. Firstly, from a molecular structure perspective, the molecular structure of alicyclic amines is relatively fixed, while the chemical bonds and reactive sites of organosilanes exhibit particularly specific patterns. This makes it difficult for them to form ideal chemical bonds during the reaction, resulting in a highly complex bonding process and uncontrollable reaction conditions. Secondly, the significant differences in their physical properties, such as solubility and polarity, make it difficult to achieve uniform dispersion in a mixed system, thus hindering effective bonding. This significantly limits the development of alicyclic aminosilane compounds in high-end applications. Summary of the Invention
[0004] To address the aforementioned technical problems, this application provides an alicyclic aminosilane compound and its preparation method. This alicyclic aminosilane compound possesses a novel 4,4-methylene double-bridged structure, and its synthesis method is simple, thus filling the gaps in existing technologies for synthesizing alicyclic aminosilane compounds.
[0005] In the first aspect, this application provides an alicyclic aminosilane compound, which adopts the following technical solution:
[0006] An alicyclic aminosilane compound, the structural formula of which is shown in formula (I):
[0007] Formula (I): R1R2R3Si-NH-Cy-CH2-Cy-NH-SiR1R2R3; where,
[0008] R1, R2, and R3 are each independently selected from C1-C6 alkyl, C6-C10 aryl, or R1 and R2 together with the silicon atoms they are attached to form a cyclic silazane structure containing 2-5 silicon atoms.
[0009] Cy represents substituted or unsubstituted cyclohexyl.
[0010] Preferably, the Cy is an unsubstituted cyclohexyl group.
[0011] Preferably, the alicyclic aminosilane compound is 4,4'-methylenebis(N-trimethylsilylcyclohexylamine), with the structural formula shown in formula (I), where R1, R2, and R3 are all methyl-CH3, and Cy is an unsubstituted cyclohexyl-C6H 10 -
[0012] Preferably, the alicyclic aminosilane compound is 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine), with the structural formula shown in (I), where R1 and R2 are both methyl-CH3, R3 is tert-butyl-C(CH3)3, and Cy is selected from unsubstituted cyclohexyl-C6H. 10 -
[0013] By employing the above-described technical solution, this application combines the saturated carbocyclic structure of alicyclic amines with silane groups to obtain a novel series of compounds with a 4,4-methylene double-bridged structure, filling a technological gap in this field. These compounds also exhibit excellent heat resistance, low volatility, strong interfacial adhesion, and good hydrophobicity. Furthermore, this application further selects unsubstituted cyclohexyl groups, reducing the possibility of steric hindrance and electronic effects caused by substituents, resulting in a more regular compound structure. This improves the stability and reactivity of the compounds, reduces side reactions during synthesis, and makes the preparation process more controllable and yields higher results.
[0014] Secondly, this application provides a method for preparing an alicyclic aminosilane compound, which employs the following technical solution:
[0015] A method for preparing an alicyclic aminosilane compound includes the following steps:
[0016] The 4,4'-methylenebicyclohexylamine or its salt shown in formula (II) is reacted with the silane compound shown in formula (III) in the presence of an inert gas and an organic solvent at a temperature between 0°C and the reflux temperature of the organic solvent. After the reaction is completed, the target product is obtained by post-treatment.
[0017] Formula (II): H2N-Cy-CH2-Cy-NH2; Formula (III): R1R2R3Si-X; where,
[0018] Cy represents substituted or unsubstituted cyclohexyl;
[0019] R1, R2, and R3 are each independently selected from C1-C6 alkyl, C6-C10 aryl, or R1 and R2 together with the silicon atoms they are attached to form a cyclic silazane structure containing 2-5 silicon atoms.
[0020] X is selected from halogen, alkoxy, or acyloxy.
[0021] Preferably, a basic reagent is added during the reaction to capture the generated acid.
[0022] Preferably, the alkaline reagent is selected from triethylamine, pyridine, N,N-diisopropylethylamine, or sodium carbonate.
[0023] Preferably, the molar ratio of 4,4'-methylenebicyclohexylamine to the silane compound is 1:(2.0-2.5).
[0024] Preferably, the silane compound is trimethylchlorosilane or tert-butyldimethylsilane.
[0025] Preferably, the organic solvent is selected from one or more of toluene, xylene, tetrahydrofuran, diethyl ether, and dichloromethane.
[0026] By adopting the above-mentioned technical solution, the reaction can be driven in the forward direction, thereby obtaining products with high yield and purity. Furthermore, the preparation method of this application uses readily available raw materials, has mild reaction conditions, and simple post-processing, making it suitable for large-scale industrial development.
[0027] In summary, this application has the following beneficial technical effects:
[0028] 1. This application combines the saturated carbide ring structure of adicyclic amine with a silane group to obtain a novel series of compounds with a 4,4-methylene double-bridged structure, filling a technological gap in this field. Moreover, these compounds possess excellent heat resistance, low volatility, strong interfacial adhesion, and good hydrophobicity.
[0029] 2. The preparation method of this application uses readily available raw materials, has mild reaction conditions, simple post-processing, and high yield and purity, making it suitable for large-scale industrial production and showing good application prospects. Attached Figure Description
[0030] Figure 1 It is the 4,4'-methylenebis(N-trimethylsilylcyclohexylamine) prepared in Example 1 of this application. 1 H-NMR test spectrum;
[0031] Figure 2 It is the 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine) prepared in Example 3 of this application. 1 H-NMR test spectrum. Detailed Implementation
[0032] To expand the field of high-performance organosilicon chemicals and advanced composite materials, this application prepares a series of alicyclic aminosilane compounds with a 4,4-methylene double-bridged structure, filling the gaps in existing technologies for synthesizing alicyclic aminosilane compounds.
[0033] The method for preparing the 4,4-methylene double-bridged dialicyclic aminosilane compound of this application includes the following steps:
[0034] 4,4'-methylenebicyclohexylamine or its salt, as shown in formula (II), is reacted with a silane compound, as shown in formula (III), in the presence of an inert gas and an organic solvent at a temperature between 0°C and the reflux temperature of the organic solvent. After the reaction is complete, post-treatment is performed to obtain the target product; Formula (II): H2N-Cy-CH2-Cy-NH2; Formula (III): R1R2R3Si-X; wherein,
[0035] Cy represents substituted or unsubstituted cyclohexyl;
[0036] R1, R2, and R3 are each independently selected from C1-C6 alkyl, C6-C10 aryl, or R1 and R2 together with the silicon atoms they are attached to form a cyclic silazane structure containing 2-5 silicon atoms.
[0037] X is selected from halogen, alkoxy, or acyloxy.
[0038] In a preferred embodiment, a basic reagent selected from triethylamine, pyridine, N,N-diisopropylethylamine, and sodium carbonate is added during the reaction to capture the generated acid. This process can drive the reaction forward and significantly increase the yield of the product.
[0039] In a preferred embodiment, the molar ratio of 4,4'-methylenebicyclohexylamine to the silane compound is 1:(2.0-2.5).
[0040] In a preferred embodiment, the silane compound is trimethylchlorosilane or tert-butyldimethylsilane.
[0041] In a preferred embodiment, the organic solvent is selected from one or more of toluene, xylene, tetrahydrofuran, diethyl ether, and dichloromethane.
[0042] Using the above preparation method, this application obtained a product with the structural formula shown in formula (I);
[0043] Formula (I): R1R2R3Si-NH-Cy-CH2-Cy-NH-SiR1R2R3; where,
[0044] R1, R2, and R3 are each independently selected from C1-C6 alkyl, C6-C10 aryl, or R1 and R2 together with the silicon atoms they are attached to form a cyclic silazane structure containing 2-5 silicon atoms.
[0045] Cy represents substituted or unsubstituted cyclohexyl.
[0046] In a preferred embodiment, the Cy is an unsubstituted cyclohexyl group. This process reduces the likelihood of steric hindrance and electronic effects caused by substituents, resulting in a more regular compound structure, which is beneficial for improving the compound's stability and reactivity. Furthermore, it reduces side reactions during synthesis, making the preparation process more controllable and yielding higher results.
[0047] Based on the foregoing, the applicant will further describe this application in detail with reference to the accompanying drawings and the following embodiments. In the specific embodiments of this application, the synthesis process is illustrated using two compound products, 4,4'-methylenebis(N-trimethylsilylcyclohexylamine) and 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine), as examples. Unless otherwise specified, the raw materials used in this application are commercially available and can be obtained conventionally.
[0048] <Example 1>
[0049] A method for preparing 4,4'-methylenebis(N-trimethylsilylcyclohexylamine) includes the following steps:
[0050] In a reaction vessel, 10 g (42.4 mmol) of 4,4'-methylenebicyclohexylamine and 200 mL of anhydrous tetrahydrofuran were added and dissolved by stirring under nitrogen protection. Triethylamine (10.4 g, 96 mmol) was added dropwise to the system, and the reaction mixture was cooled to 0 °C. Trimethylchlorosilane (9.7 g, 96 mmol) was slowly added dropwise at 0–5 °C. After the addition was complete, the ice bath was removed, and the reaction mixture was gradually heated to room temperature and stirred for 12 h at room temperature. After the reaction was complete, the white solid triethylamine hydrochloride was removed by filtration. The filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1) to give 14.2 g of a colorless, transparent, oily liquid product, with a yield of 83%.
[0051] from Figure 1 The characterization data of this product can be seen as follows: 1 H-NMR (CDCl3, 400MHz): δ (0.012~-0.063ppm), (C H 3)6; δ (0.825~1.840ppm), -C5 H9 -C H 2-C5 H 9-; δ (2.485 ppm), -NH-C H -; δ (2.853ppm), -N H -
[0052] <Example 2>
[0053] A method for preparing 4,4'-methylenebis(N-trimethylsilylcyclohexylamine) includes the following steps:
[0054] In a reaction vessel, 17.4 g (83 mmol) of 4,4'-methylenebicyclohexylamine and 250 mL of anhydrous toluene were added and dissolved by stirring under nitrogen protection. Triethylamine (16.7 g, 165 mmol) was added dropwise to the system, and the reaction mixture was cooled to 0 °C. Trimethylchlorosilane (17.9 g, 165 mmol) was slowly added dropwise at 0–5 °C. After the addition was complete, the ice bath was removed, and the reaction mixture was gradually heated to room temperature and stirred for 24 h at room temperature. After the reaction was complete, the white solid triethylamine hydrochloride was removed by filtration. The filtrate was concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1) to give 26.4 g of a colorless, transparent, oily liquid product, with a yield of 90%.
[0055] <Example 3>
[0056] A method for preparing 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine) includes the following steps:
[0057] In a reaction vessel, 10.0 g (48 mmol) of 4,4'-methylenebicyclohexylamine and 200 mL of anhydrous toluene were added and stirred to dissolve under nitrogen protection. N,N-diisopropylethylamine (13.5 g, 105 mmol) was then added to the system, followed by 15.7 g (105 mmol) of tert-butyldimethylchlorosilane at room temperature. After the addition was complete, the reaction system was heated to 80 °C and refluxed for 6 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to remove insoluble matter, and the filtrate was washed successively with saturated sodium bicarbonate solution and brine. The organic phase was dried over anhydrous sodium sulfate. After drying, the filtrate was concentrated under reduced pressure to obtain a pale yellow viscous liquid, which was then purified by high-vacuum distillation to obtain 14.5 g of a colorless, transparent liquid product, with a yield of 85%.
[0058] from Figure 2 The characterization data of this product can be seen as follows: 1 H-NMR (CD3COCD3, 400MHz): δ (0.002~0.012ppm), Si-(C H 3)4; δ (1.000~1.900ppm), -C5 H9 -C H 2-C5 H 9-,2(Si-C-(C H 3)3); δ(2.537ppm), -NH-C H -; δ (2.977ppm), -N H -
[0059] <Example 4>
[0060] A method for preparing 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine) includes the following steps:
[0061] In a reaction vessel, 10.0 g (48 mmol) of 4,4'-methylenebicyclohexylamine and 150 mL of anhydrous toluene were added and stirred to dissolve under nitrogen protection. Imidazole (7.1 g, 105 mmol) was added to the system, followed by 15.8 g (105 mmol) of tert-butyldimethylchlorosilane at room temperature. After the addition was complete, the reaction system was heated to 80 °C and refluxed for 6 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to remove insoluble matter, and the filtrate was washed successively with saturated sodium bicarbonate solution and brine. The organic phase was dried over anhydrous sodium sulfate. After drying, the filtrate was concentrated under reduced pressure to obtain a pale yellow viscous liquid, which was then purified by high-vacuum distillation to obtain 11.1 g of a colorless, transparent liquid product, with a yield of 65%.
[0062] <Example 5>
[0063] A method for preparing 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine) includes the following steps:
[0064] In a reaction vessel, 21.0 g (100 mmol) of 4,4'-methylenebicyclohexylamine, 20.2 g (200 mmol) of anhydrous triethylamine, and 200 g of anhydrous toluene were added and stirred to dissolve. At room temperature, 30.14 g (200 mmol) of tert-butyldimethylchlorosilane was added to the system. After the addition was complete, the reaction system was stirred at room temperature for 24 h. After the reaction was complete, insoluble matter was removed by filtration, and the filtrate was obtained. The filtrate was concentrated under normal pressure to obtain a light yellow viscous liquid, which was then purified by high-vacuum distillation to obtain 30.3 g of a colorless, transparent liquid product, with a yield of 69%.
[0065] Data Analysis
[0066] Data from Examples 1-5 and appendices Figure 1-2 As can be seen, this application has indeed prepared a dialicyclic aminosilane compound with a 4,4-methylene double-bridged structure by combining the saturated carbocyclic structure of the dialicyclic amine with a silane group. This compound has a novel structure, filling a technological gap in this field, and possesses excellent heat resistance, low volatility, strong interfacial adhesion, and good hydrophobicity. Furthermore, the preparation method of this application uses readily available raw materials, mild reaction conditions, simple post-processing, and a high yield, making it suitable for large-scale industrial production.
[0067] The embodiments described in this specific implementation are preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.
Claims
1. An alicyclic aminosilane compound, characterized in that, Its structural formula is shown in equation (I): Formula (I): R1R2R3Si-NH-Cy-CH2-Cy-NH-SiR1R2R3; where, R1, R2, and R3 are each independently selected from C1-C6 alkyl, C6-C10 aryl, or R1 and R2 together with the silicon atoms they are attached to form a cyclic silazane structure containing 2-5 silicon atoms. Cy represents substituted or unsubstituted cyclohexyl.
2. The alicyclic aminosilane compound according to claim 1, characterized in that, The Cy is an unsubstituted cyclohexyl group.
3. The alicyclic aminosilane compound according to claim 2, characterized in that, The alicyclic aminosilane compound is 4,4'-methylenebis(N-trimethylsilylcyclohexylamine), and its structural formula is shown in formula (I), where R1, R2, and R3 are all methyl-CH3, and Cy is an unsubstituted cyclohexyl-C6H 10 - 4. The alicyclic aminosilane compound according to claim 2, characterized in that, The alicyclic aminosilane compound is 4,4'-methylenebis(N-tert-butyldimethylsilylcyclohexylamine), with the structural formula shown in (I), where R1 and R2 are both methyl-CH3, R3 is tert-butyl-C(CH3)3, and Cy is selected from unsubstituted cyclohexyl-C6H. 10 - 5. A method for preparing an alicyclic aminosilane compound according to any one of claims 1-4, characterized in that, Includes the following steps: The 4,4'-methylenebicyclohexylamine or its salt shown in formula (II) is reacted with the silane compound shown in formula (III) in the presence of an inert gas and an organic solvent at a temperature between 0°C and the reflux temperature of the organic solvent. After the reaction is completed, the target product is obtained by post-treatment. Formula (II): H2N-Cy-CH2-Cy-NH2; Formula (III): R1R2R3Si-X; where, Cy represents substituted or unsubstituted cyclohexyl; R1, R2, and R3 are each independently selected from C1-C6 alkyl, C6-C10 aryl, or R1 and R2 together with the silicon atoms they are attached to form a cyclic silazane structure containing 2-5 silicon atoms. X is selected from halogen, alkoxy, or acyloxy.
6. The method for preparing an alicyclic aminosilane compound according to claim 5, characterized in that, A basic reagent is added during the reaction to capture the generated acid.
7. The method for preparing an alicyclic aminosilane compound according to claim 6, characterized in that, The alkaline reagent is selected from triethylamine, pyridine, N,N-diisopropylethylamine, or sodium carbonate.
8. The method for preparing an alicyclic aminosilane compound according to claim 5, characterized in that, The molar ratio of 4,4'-methylenebicyclohexylamine to the silane compound is 1:(2.0-2.5).
9. The method for preparing an alicyclic aminosilane compound according to claim 5, characterized in that, The silane compound is trimethylchlorosilane or tert-butyldimethylsilane.
10. The method for preparing an alicyclic aminosilane compound according to claim 5, characterized in that, The organic solvent is selected from one or more of toluene, xylene, tetrahydrofuran, diethyl ether, and dichloromethane.