Preparation method of silicon-acrylate compound
By leveraging the synergistic effect of ruthenium catalyst and hydrogen absorber, the problem of Si-C bond instability was solved, enabling the efficient and low-cost synthesis of silicon-acrylate compounds, providing stable material properties and economic benefits.
Patent Information
- Application Number
- CN202511018655.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-23
- Publication Date
- 2025-11-21
AI Technical Summary
In the traditional reaction of acrylates with organosilicon to prepare silicon-acrylate compounds using platinum catalysts, the Si-C bonds are unstable and easily break under acidic or alkaline conditions, affecting the material properties.
The synthesis of silicon-acrylate compounds was achieved by using a ruthenium catalyst and a hydrogen absorber in the presence of a solvent, through the dehydrogenation coupling reaction of acrylate compounds containing terminal olefins with organohydrosilanes via the C-Si bond.
The synthesis of more stable silicon-acrylate compounds reduced catalyst costs, increased synthesis yields, simplified the operation process, and reduced capital and labor inputs for industrial production.
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Figure CN120987991A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a preparation method of a silicon-acrylate compound. BACKGROUND
[0002] Organosilicon compounds refer to a kind of compounds containing C-Si bonds in molecules or between molecules. This kind of compound material has good material properties such as corrosion resistance, low surface tension and good waterproof performance, and is widely developed in the fields of manufacturing national defense and military materials, silicon-based functional materials for construction, and biological reagents. In the past nearly two decades, the synthesis of various functional organosilicon molecules has been continuously improved through transition metal-catalyzed C-H bond activation, including nucleophilic substitution, cross-coupling, hydrosilylation and the like. Some synthesized silicon-containing compounds even exhibit higher biological activity than the parent carbon compounds. Therefore, the synthesis of silicon-containing compounds has always been a research hotspot in the fields of organic synthesis chemistry and material chemistry.
[0003] Acrylate-modified organosilicon compounds can further improve the lubricity, brightness, softness, water and oil repellency and antifouling performance of silicone products, because the acrylate groups increase the compatibility of siloxane segments and organic polymers while retaining the excellent properties of organosilicon itself, such as the products BYK-355 and BYK-331 of Germany. In addition, the acrylate groups also have photo-reactivity, so the acrylate-modified organosilicon resin can improve the leveling property and adhesion of the material, and the acrylate-modified organosilicon material can be used as an important waterproof base material. However, the traditional reaction of acrylate with organosilicon is usually prepared by platinum catalyst (such as Karstedt catalyst) through silicon-hydrogen addition, thereby preparing a silicon-modified acrylate compound. However, the Si-C bond of this kind of compound is unstable and can be easily broken under acidic or basic conditions, thereby affecting the performance of the material.
[0004] Therefore, it is urgent to explore a new preparation method of a silicon-acrylate compound. SUMMARY
[0005] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the first aspect of the present application provides a preparation method of a silicon-acrylate compound, which has simple raw materials, high synthesis yield and low cost.
[0006] According to the first aspect of the present application, a preparation method of a silicon-acrylate compound is provided, which comprises the following steps:
[0007] In the presence of a solvent, compound I, compound II, a ruthenium catalyst and a hydrogen absorber are mixed and heated to react to obtain compound III;
[0008] wherein the compound I, the compound II, and the compound III have the following structural formulae:
[0009]
[0010] R1, R2, R3are each independently selected from C 1～6 alkyl, C 3～8 siloxyl;
[0011] R4is selected from C 1～6 alkyl, C 1～6 alkyl, phenyl or phenyl substituted with C 1～6 alkyl, benzyl.
[0012] According to a preferred embodiment of the present application, the ruthenium catalyst is selected from at least one of dodecyltriruthenium, dichloro(p-methylcumene)ruthenium(II) dimer, tris(triphenylphosphine)ruthenium dichloride, tris(triphenylphosphine)carbonylhydrido ruthenium or tris(triphenylphosphine)carbonylhydrido chloro ruthenium.
[0013] According to a preferred embodiment of the present application, the ruthenium catalyst is selected from at least one of tris(triphenylphosphine)carbonylhydrido ruthenium, tris(triphenylphosphine)carbonylhydrido chloro ruthenium, dichloro(p-methylcumene)ruthenium(II) dimer. These catalysts are more prone to oxidation reaction with Si-H, thus facilitating the reaction, and therefore, the yield of the reaction can be further improved.
[0014] According to a preferred embodiment of the present application, the hydrogen absorbent is selected from at least one of norbornene, norbornadiene, α-methylstyrene or cyclohexene. In this way, the hydrogen absorbent plays a role in forming an active ruthenium catalyst with ruthenium on the one hand, and absorbing the hydrogen generated in the dehydrogenative coupling reaction in the catalytic cycle on the other hand, thus improving the yield.
[0015] According to a preferred embodiment of the present application, the molar ratio of the compound I, the compound II, the ruthenium catalyst and the hydrogen absorbent is 1:(1-5):(0.01-0.20):(2-6).
[0016] According to a preferred embodiment of the present application, the molar ratio of the compound I, the compound II, the ruthenium catalyst and the hydrogen absorbent is 1:1.2:0.02:4.
[0017] According to a preferred embodiment of the present application, the heating reaction is carried out at a temperature of 50-150°C. For example, the reaction temperature is 50°C, 70°C, 80°C, 90°C, 100°C, 120°C, 150°C or any sub-range formed by any two of the above-mentioned values.
[0018] According to a preferred embodiment of the present application, the heating reaction is carried out for 1-10 hours.
[0019] According to a preferred embodiment of the present application, the heating reaction is carried out at a temperature of 70-100°C.
[0020] According to a preferred embodiment of the present application, the heating reaction is carried out for 1-5 hours.
[0021] According to a preferred embodiment of the present application, the solvent is at least one selected from cyclohexane, 1,4-dioxane, dimethyl carbonate, N,N-dimethylformamide or toluene.
[0022] According to a preferred embodiment of the present application, the heating reaction is carried out under anaerobic conditions.
[0023] According to a preferred embodiment of the present application, the heating reaction is carried out under anhydrous conditions.
[0024] The preparation method according to the embodiments of the present application has at least the following beneficial effects:
[0025] The present application selects a ruthenium catalyst with lower catalytic activity and lower price to carry out the C-Si bond dehydrogenation coupling reaction of the acrylic ester compound containing terminal olefin and organic hydrosilane: not only can the tandem silicon-hydrogen addition reaction and C-Si bond coupling reaction of the acrylic ester compound containing terminal olefin and silicon hydride be realized, a new type of silicon-acrylic ester compound is obtained, the synthesis method of the silicon-acrylic ester compound is enriched, and a more stable silicon-acrylic ester compound is synthesized. Moreover, the present application has the advantages of simple starting material, high synthesis yield, and convenient operation process. The present application creatively uses a relatively low-cost ruthenium catalyst to catalytically synthesize a silicon-acrylic ester compound under the condition of adding an unsaturated olefin. Except for the final product, the intermediates in a series of conversion processes do not need to be separated and purified, only one reaction step is needed, the amount of ruthenium catalyst used is small, and the price is relatively low, which reduces the investment of funds and labor for industrial production. In addition, the catalytic method can provide theoretical support for the synthesis of silicon-acrylic ester resins.
[0026] Definitions and general terms
[0027] "C 1-6 alkyl" refers to an alkyl group having a total number of carbon atoms of 1-6, including C 1-6 linear alkyl groups, C 1-6 branched alkyl groups and C 3-6"Alkyl" means a straight chain alkyl group, a branched chain alkyl group or a cyclic alkyl group having a total number of carbon atoms of 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. For example, an alkyl group can be a straight chain alkyl group having a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, a branched chain alkyl group having a total number of carbon atoms of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or a cyclic alkyl group having a total number of carbon atoms of 3, 4, 5, 6, 7, 8, 9 or 10. For example, an alkyl group can be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, an ethylcyclopropyl group, a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, and the like.
[0028] "C 3～8 "Siloxyl" means a siloxyl group having a total number of carbon atoms of 3 to 8, for example, including the following structures:
[0029]
[0030] Additional features and advantages of the application will be set forth in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following or can be learned by practice of the application. BRIEF DESCRIPTION OF DRAWINGS
[0031] The foregoing and / or additional aspects and advantages of the present application are achieved by providing a method for producing a compound represented by the following formula (I):
[0032] Figure 1 NMR (H) of the product produced in Example 1 of the present application;
[0033] Figure 2 NMR (C) of the product produced in Example 1 of the present application;
[0034] Figure 3 NMR (H) of the product produced in Example 6 of the present application;
[0035] Figure 4 NMR (C) of the product produced in Example 6 of the present application;
[0036] Figure 5 NMR (H) of the product produced in Example 7 of the present application;
[0037] Figure 6 NMR (C) of the product produced in Example 7 of the present application;
[0038] Figure 7 NMR (H) of the product produced in Example 8 of the present application;
[0039] Figure 8 NMR (C) of the product produced in Example 8 of the present application;
[0040] Figure 9 NMR (C) of the product produced in Example 9 of the present application;
[0041] Figure 10 The product prepared in Example 9 of the present application was subjected to nuclear magnetic resonance hydrogen spectrum. DETAILED DESCRIPTION
[0042] The following are specific examples of the present application, and the technical solutions of the present application are further described in combination with the examples, but the present application is not limited to these examples.
[0043] The reagents, methods and equipment used in the present application are all conventional reagents, methods and equipment in the technical field unless otherwise specified.
[0044] Some of the raw materials used in the examples of the present application are as follows:
[0045] Benzyl acrylate, phenyl acrylate, 2-phenoxyethyl acrylate, 4-ethylphenyl acrylate: purchased from Ron Chemical Co., Ltd., Shanghai Bide Pharmaceutical Technology Co., Ltd.
[0046] Triethylsilane: purchased from Shanghai Maikelin Biochemical Technology Co., Ltd.
[0047] Tris(triphenylphosphine)carbonyl dihydrido ruthenium, tris(triphenylphosphine) dichloro ruthenium, hexahydrate tris(2,2'-bipyridine) dichloro ruthenium, dichloro(p-methylisopropylbenzene) ruthenium(II) dimer, tris(triphenylphosphine) carbonyl hydrochloride ruthenium: purchased from Anhui Zesheng Technology Co., Ltd., Shanghai Bide Pharmaceutical Technology Co., Ltd.
[0048] Norbornene, norbornadiene, α-methylstyrene, cyclohexene: purchased from Anhui Zesheng Technology Co., Ltd., Shanghai Bide Pharmaceutical Technology Co., Ltd., Shanghai Aladdin Reagent Co., Ltd.
[0049] Example 1
[0050] This example provides a preparation method of a silicon-acrylate compound, and the reaction equation and steps are as follows:
[0051]
[0052] In a 20 mL Schlenk tube, benzyl acrylate (37.5 μL, 0.25 mmol), triethylsilane (47.9 μL, 0.3 mmol), norbornene (94.2 mg, 1.0 mmol), and catalyst tris(triphenylphosphine) carbonyl hydrochloride ruthenium (4.76 mg, 0.005 mmol) were sequentially added, and the reaction was carried out under the conditions of solvent dimethyl carbonate (1.0 mL) and nitrogen, with electromagnetic stirring (500-800 rpm, 550 rpm was used in this example) at a reaction temperature of 80°C, for 2 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography using ethyl acetate and petroleum ether as the eluent. A light purple oil (63 mg, 91%) was obtained after separation.
[0053] Example 2
[0054] Example 2 also provides a preparation method of the silicon-acrylate compound, the preparation method and raw materials of which are the same as those of Example 1, except that the solvent is cyclohexane; and the yield is 78%.
[0055] Example 3
[0056] Example 3 also provides a preparation method of the silicon-acrylate compound, the preparation method and raw materials of which are the same as those of Example 1, except that the hydrogen absorbent is α-methylstyrene; and the yield is 34%.
[0057] Example 4
[0058] Example 4 also provides a preparation method of the silicon-acrylate compound, the preparation method and raw materials of which are the same as those of Example 1, except that the ruthenium catalyst is tris(triphenylphosphine)carbonyl ruthenium hydride; and the yield is 42%.
[0059] Example 5
[0060] Example 5 also provides a preparation method of the silicon-acrylate compound, the preparation method and raw materials of which are the same as those of Example 1, except that the reaction temperature is 120°C; and the yield is 61%.
[0061] The products prepared in Examples 1-5 are respectively subjected to qualitative detection by nuclear magnetic resonance (NMR), and it is found that the product detection data are consistent, and the specific results are as follows:
[0062] 1 H NMR (400 MHz, CDCI3): as shown in Figure 1 δ (ppm) = 7.45-7.36 (m, 5H), 7.33 (d, J = 19.2 Hz, 1H), 6.36 (d, J = 19.2 Hz, 1H), 5.23 (s, 2H), 0.99 (t, J = 8.0 Hz, 9H), 0.71-0.65 (m, 6H).
[0063] Other parameters during the test are as follows: temperature: 294.4; pulse sequence: zg30; number of scans: 16; receiver gain: 101; relaxation delay: 1.0000; pulse width: 9.7200; spectrometer frequency: 500.15; spectral width: 10000.0; lowest frequency: -1911.6; nucleus: 1 H; acquired size: 32768; spectral size: 65536.
[0064] 13 C NMR (101 MHz, CDCl3): delta (ppm) = 165.6, 147.6, 136.0, 134.7, 128.6, 128.4, 128.3, 66.4, 7.2, 3.0 as shown. Figure 2
[0065] Other parameters during the test are as follows: temperature: 294.9; pulse sequence: zgpg30; number of scans: 100; receiver gain: 101; relaxation delay: 2.0000; pulse width: 10.0000; spectrometer frequency: 125.78; spectral width: 30120.5; lowest frequency: -2465.0; nucleus: 13C; acquired size: 32768; spectral size: 65536.
[0066] From the yield comparison of examples 1 to 5, when the silicon-alkenoate compound is prepared by using the scheme of the present application, a higher yield level can be achieved, and since the price of the ruthenium catalyst used is significantly lower than that of the rhodium and iridium catalysts (about one tenth), therefore, compared with the synthesis method of the related art, significant progress can still be made in economic benefits.
[0067] Example 6
[0068] Example 6 provides a method for preparing a silicon-acrylate compound, the reaction equation and preparation steps are as follows:
[0069]
[0070] In a 20 mL Schlenk tube, phenyl acrylate (34.4 μL, 0.25 mmol), triethylsilane (47.9 μL, 0.3 mmol), norbornene (94.2 mg, 1.0 mmol), catalyst tris(triphenylphosphine)carbonyl hydridochlororuthenium (4.76 mg, 0.005 mmol) were added successively, under the condition of solvent dimethyl carbonate (1.0 mL) and nitrogen, the reaction was carried out under electromagnetic stirring (500-800 rpm, 550 rpm was used in this example) at 80 °C, the reaction time was 2 hours, after the reaction was completed, the solvent was removed by rotary evaporation, the mixture was separated by column chromatography, the eluent was ethyl acetate and petroleum ether, and white oil (54 mg, 82%) was obtained after separation.
[0071] The product prepared in Example 6 was subjected to NMR qualitative detection, and the product detection data are as follows:
[0072] 1 H NMR (400 MHz, CDC13): as shown in Figure 3 δ (ppm) = 7.51-7.40 (m, 3H), 7.27 (t, J = 7.2 Hz, 1H), 7.17 (d, J = 6.8 Hz, 2H), 6.51 (d, J = 18.8 Hz, 1H), 1.03 (t, J = 8.0 Hz, 9H), 0.76-0.70 (m, 6H).
[0073] Other parameters during the test are as follows: temperature: 294.6; pulse sequence: zg30; number of scans: 16; receiver gain: 101; relaxation delay: 1.0000; pulse width: 9.7200; spectrometer frequency: 500.15; spectral width: 10000.0; lowest frequency: -1911.6; nucleus: 1 H; acquired size: 32768; spectral size: 65536.
[0074] 13 C NMR (101 MHz, CDC13): δ (ppm) = 164.0, 150.9, 149.6, 134.2, 129.4, 125.8, 121.6, 7.2, 3.0. Figure 4
[0075] Other parameters during the test are as follows: temperature: 294.8; pulse sequence: zgpg30; number of scans: 100; receiver gain: 101; relaxation delay: 2.0000; pulse width: 10.0000; spectrometer frequency: 125.78; spectral width: 30120.5; lowest frequency: -2465.0; nucleus: 13C; acquired size: 32768; spectral size: 65536.
[0076] Example 7
[0077] Example 7 provides a preparation method of a silicon-acrylate compound, the reaction equation and preparation steps are as follows:
[0078]
[0079] In a 20 mL Schlenk tube, 2-phenoxyethyl acrylate (43.5 μL, 0.25 mmol), triethylsilane (47.9 μL, 0.3 mmol), norbornene (94.2 mg, 1.0 mmol), catalyst tris(triphenylphosphine)carbonyl hydridochlororuthenium (4.76 mg, 0.005 mmol) were added in sequence, under the condition of solvent dimethyl carbonate (1.0 mL) and nitrogen, electromagnetic stirring (500-800 rpm, 550 rpm was used in this example) was carried out at 80 °C, the reaction time was 2 hours, after the reaction was completed, the solvent was removed by rotary evaporation, the mixture was separated by column chromatography, the eluent was ethyl acetate and petroleum ether, and white oil (54 mg, 70%) was obtained after separation.
[0080] The product prepared in Example 7 was subjected to NMR qualitative detection, and the product detection data are as follows:
[0081] 1 H NMR (400MHz, CDCl3): such as Figure 5 As shown, δ (ppm) = 7.42-7.23 (m,, 3H), 7.05-6.86 (m, 3H), 6.35 (d, J = 19.1Hz, 1H), 4.5 9-4.49(m,2H),4.29-4.20(m,2H),0.98(t,J=8.0Hz,9H),0.67(q,J=7.9Hz,6H).
[0082] Other parameters during the test are as follows: Temperature: 294.5°C; Pulse sequence: ZG30; Number of scans: 16; Receiver gain: 101; Relaxation delay: 1.0000; Pulse width: 9.7200; Spcttrometer frequency: 500.15; Spectral width: 10000.0; Lowest frequency: -1911.6; Nucleus: 1 H; Acquired size: 32768; Spectral size: 65536.
[0083] 13 C NMR (101MHz, CDCl3): such as Figure 6 As shown, δ(ppm) = 165.6, 158.5, 147.9, 134.5, 129.5, 121.2, 114.7, 65.9, 63.0, 7.2, 3.0.
[0084] Other parameters during the test are as follows: temperature: 294.2; pulse sequence: zgpg30; number of scans: 100; receiver gain: 101; relaxation delay: 2.0000; pulse width: 10.0000; spectrometer frequency: 125.78; spectral width: 30120.5; lowest frequency: -2465.0; nucleus: 13C; acquired size: 32768; spectral size: 65536.
[0085] Example 8
[0086] Example 8 provides a preparation method of a silicon-acrylate compound, the reaction equation and the preparation steps are shown as follows:
[0087]
[0088] In a 20 mL Schlenk tube, 4-ethylphenyl acrylate (42.9 μL, 0.25 mmol), triethylsilane (47.9 μL, 0.3 mmol), norbornene (94.2 mg, 1.0 mmol), catalyst tris(triphenylphosphine)carbonyl hydridochlororuthenium (4.76 mg, 0.005 mmol) were added successively, and the reaction was carried out under the conditions of solvent dimethyl carbonate (1.0 mL) and nitrogen, the reaction temperature was 80°C, and electromagnetic stirring (500-800 rpm, 550 rpm was used in this example) was carried out for 2 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography, and the eluent was ethyl acetate and petroleum ether. After separation, white oil (52 mg, 72%) was obtained.
[0089] The product prepared in Example 8 was subjected to NMR qualitative detection, and the product detection data are as follows:
[0090] 1 H NMR (400 MHz, CDCI3): as Figure 7shown δ (ppm) = 7.46 (d, J = 19.1 Hz, 1H), 7.27-7.02 (m, 4H), 6.49 (d, J = 19.0 Hz, 1H), 2.68 (q, J = 7.6 Hz, 2H), 1.27 (t, J = 7.5 Hz, 3H), 1.02 (t, J = 8.0 Hz, 9H), 0.72 (q, J = 7.9 Hz, 6H).
[0091] Other parameters during the test were as follows: temperature: 294.5; pulse sequence: zg30; number of scans: 16; receiver gain: 101; relaxation delay: 1.0000; pulse width: 9.7200; spectrometer frequency: 500.15; spectral width: 10000.0; lowest frequency: -1911.6; nucleus: 1 H; acquired size: 32768; spectral size: 65536.
[0092] 13 C NMR (101 MHz, CDC13): δ (ppm) = 164.3, 149.4, 148.7, 141.7, 134.3, 128.8, 121.2, 28.3, 15.6, 7.2, 3.0. Figure 8
[0093] Other parameters during the test are as follows: temperature: 294.8; pulse sequence: zgpg30; number of scans: 100; receiver gain: 101; relaxation delay: 2.0000; pulse width: 10.0000; spectrometer frequency: 125.78; spectral width: 30120.5; lowest frequency: -2465.0; nucleus: 13C; acquired size: 32768; spectral size: 65536.
[0094] Example 9
[0095] Example 9 provides a preparation method of a silicon-acrylate compound, the reaction equation and the preparation steps are shown as follows:
[0096] In a 20 mL Schlenk tube, benzyl acrylate (37.5 μL, 0.25 mmol), methyl-bis(trimethylsiloxy)silane (81.5 μL, 0.3 mmol), norbornene (94.2 mg, 1.0 mmol), catalyst tris(triphenylphosphine)carbonyl hydridochlororuthenate (4.76 mg, 0.005 mmol) were added successively, under the condition of solvent dimethyl carbonate (1.0 mL) and nitrogen, electromagnetic stirring (500-800 rpm, 550 rpm was used in this example) was carried out at 80 °C, the reaction time was 2 hours, after the reaction was completed, the solvent was removed by rotary evaporation, the mixture was separated by column chromatography, the eluent was ethyl acetate and petroleum ether, and white oil (84 mg, 88%) was obtained after separation.
[0097] The product prepared in Example 9 was subjected to NMR qualitative detection, and the product detection data are as follows:
[0098] 1 H NMR (400 MHz, CDCI3): as shown in Figure 9
[0099] Other parameters during the test were as follows: temperature: 294.5; pulse sequence: zg30; number of scans: 16; receiver gain: 101 ; relaxation delay: 1.0000; pulse width: 9.7200; spectrometer frequency: 500.15; spectral width: 10000.0; lowest frequency: -1911.6; nucleus: 1H; acquired size: 32768; spectral size: 65536. 1 Other parameters during the test were as follows: temperature: 294.5; pulse sequence: zg30; number of scans: 16; receiver gain: 101 ; relaxation delay: 1.0000; pulse width: 9.7200; spectrometer frequency: 500.15; spectral width: 10000.0; lowest frequency: -1911.6; nucleus: 1H; acquired size: 32768; spectral size: 65536.
[0100] 13 C NMR (101 MHz, CDC13): δ (ppm) = 165.9, 146.3, 136.0, 134.6, 128.6, 128.3, 128.3, 66.4, 1.8, 0.3. Figure 10
[0101] Other parameters during the test were as follows: temperature: 294.8; pulse sequence: zgpg30; number of scans: 100; receiver gain: 101 ; relaxation delay: 2.0000; pulse width: 10.0000; spectrometer frequency: 125.78; spectral width: 30120.5; lowest frequency: -2465.0; nucleus: 13C; acquired size: 32768; spectral size: 65536.
[0102] In summary, the application provides a new synthetic route for synthesis of sila-alkenoate compounds, provides a technical basis for development of functional organic silicon materials, and the prepared sila-alkenoate compounds have dual characteristics of organic silicon and acrylate, can be used as potential waterproof material additives, improve the leveling property and adhesion of the material, and improve the lubricity, brightness, softness, water and oil repellency and antifouling performance of the silicone oil product. Meanwhile, due to the retention of C=C bond and COO- bond, the sila-alkenoate compounds can be used as intermediates in fine chemical conversion engineering.
[0103] The above is described in detail in combination with the embodiments of the application, but the application is not limited to the above embodiments, and various changes can be made within the knowledge range possessed by those skilled in the art without departing from the purpose of the application.
Claims
1. A method for producing a silicon-acrylate compound, characterized by, The method comprises the following steps: Compound I, compound II, ruthenium catalyst and hydrogen absorbent are mixed and heated to react in the presence of a solvent to obtain compound III; The structural formula of the compound I, the compound II and the compound III are as follows: R1, R2, R3are each independently selected from the group consisting of C 1～6 alkyl, C 3～8 siloxyl; R4is selected from C 1～6 alkyl, phenoxy-substituted C 1～6 alkyl, phenyl or phenyl substituted by C 1～6 alkyl, phenyl, benzyl.
2. The method for producing a silicon-acrylate compound according to claim 1, characterized by, The ruthenium catalyst is at least one selected from dodecyltriruthenium, dichloro(p-methylisopropylbenzene) ruthenium (II) dimer, tris(triphenylphosphine) ruthenium dichloride, tris(triphenylphosphine) carbonyl hydride ruthenium or tris(triphenylphosphine) carbonyl hydrogen chloride ruthenium.
3. The method for producing a silicon-acrylate compound according to claim 1, characterized by, The hydrogen absorbent is at least one selected from norbornene, norbornadiene, alpha-methyl styrene or cyclohexene.
4. The method for producing a silicon-acrylate compound according to claim 1, characterized by, The molar ratio of the compound I, the compound II, the ruthenium catalyst and the hydrogen absorbent is 1:(1-5):(0.01-0.20):(2-6).
5. The method for preparing a silicon-acrylate compound according to claim 1, characterized by, The temperature of the heating reaction is 50-150 DEG C.
6. The method for preparing a silicon-acrylate compound according to claim 1, wherein The time of the heating reaction is 1-10 h.
7. The method for producing a silicon-acrylate compound according to claim 1 or 5, characterized by, The temperature of the heating reaction is 70-100 DEG C.
8. The method for producing a silicon-acrylate compound according to claim 1 or 6, characterized by, The time of the heating reaction is 1-5 h.
9. The method for preparing a silicon-acrylate compound according to claim 1, wherein The solvent is at least one selected from cyclohexane, 1,4-dioxane, dimethyl carbonate, N, N-dimethylformamide or toluene.
10. The method for preparing a silicon-acrylate compound according to claim 1, characterized by, The heating reaction is carried out under an oxygen-free condition.