A method for the iron-catalyzed sulfur-functionalization of silanes, siloxanes or polysiloxanes

Abstract

This invention belongs to the technical field of C-H bond functionalization and sulfur-functionalized polymer material preparation of organosilicon compounds, and discloses a method for preparing iron-catalyzed sulfur-functionalized silanes, siloxanes, or polysiloxanes. This method uses α-silicon-containing C(sp...)... 3 Using silanes, siloxanes, or polysiloxanes with α-H bonds as substrates, and under conditions of additives, catalysts, solvents, and light irradiation, C-S bonds are directly constructed at the α-silyl alkyl sites to obtain α-silyl sulfide functionalized products. This invention eliminates the need for pre-activation of inert C(sp) groups. 3 The α-H bond does not rely on precious metal catalysts. The reaction is mild, the steps are simple, the atom economy is high, and the substrates are widely applicable. It can realize the efficient and controllable sulfide functionalization of small to high molecular weight silanes, and has good industrial application prospects in the field of organosilicon functional materials.

Description

Technical Field

[0001] This invention belongs to the field of preparation technology of organosilicon compound CH bond functionalization and sulfur-functionalized polymer materials. It discloses an iron-catalyzed method for preparing sulfur-functionalized silanes, siloxanes, or polysiloxanes, specifically involving a light-mediated iron-catalyzed sulfinate-involved α-silyl C(sp) group of silanes, siloxanes, or polysiloxanes. 3 )-H bond sulfur functionalization method. Background Technology

[0002] Organosilicon compounds are widely used in home furnishings, automobiles, electronic packaging, medical care, flexible materials, and high-end functional materials due to their excellent thermal stability, mechanical stability, chemical corrosion resistance, low surface energy, and low toxicity. Silanes, siloxanes, and polysiloxanes are important building blocks of organosilicon materials, and their backbones or side chains typically contain a large number of nonpolar alkyl groups such as methyl and ethyl groups.

[0003] In the prior art, the functionalization methods for nonpolar alkyl sites in silanes, siloxanes, or polysiloxanes are relatively limited. To achieve further transformation of these sites, it is usually necessary to first functionalize C(sp...) 3 Pre-activation of the -H bond can be achieved through methods such as halogenation, metallization, introduction of directing groups, or pre-construction of reactive functional groups. However, these methods typically suffer from cumbersome procedures, poor atom economy, sensitivity to reaction conditions, and high catalytic system costs, hindering resource conservation and green synthesis.

[0004] Current methods for CH functionalization of alkanes primarily rely on noble metal catalysts, which are not suitable for polysiloxane systems. In recent years, ligand-metal charge transfer (LMCT) processes have been used to achieve inert C(sp...) functionalization. 3 The direct functionalization of the C(sp)-H bond has attracted widespread attention. Abundant transition metals can generate carbon radical intermediates under photoluminescence, thereby achieving subsequent functionalization transformations. However, applying this strategy to siloxane or polysiloxane systems still faces many challenges, such as the nonpolar C(sp)-H bond. 3 It has high H-bond dissociation energy, is difficult to control regioselectivity, and has limited compatibility with functionalized reagents. Summary of the Invention

[0005] Regarding the existing technology of silane / siloxane / polysiloxane alkyl C(sp) 3 The functionalization of α-H bonds requires pre-activation, depends on noble metal catalysts, requires harsh reaction conditions, has a narrow substrate applicability range, and cannot achieve controllable post-modification of polymeric polysiloxanes. This invention provides an iron-catalyzed, light-mediated method that achieves α-position functionalization of silanes / siloxanes / polysiloxanes in one step without pre-activation.

[0006] Furthermore, this invention provides a method for synthesizing functionalized silanes, siloxanes, or polysiloxanes by using iron-catalyzed sulfinates in a reaction under light irradiation. This method eliminates the need for inert C(sp) salts. 3 Pre-activation of the -H bond is achieved without high-temperature conditions. C–S bonds can be constructed at the alkyl sites of silanes, siloxanes, or polysiloxanes under mild conditions using abundant metallic iron catalysis, thereby obtaining functionalized silanes, siloxanes, or polysiloxanes. This method offers advantages such as mild reaction conditions, a wide range of applicable raw materials, simple steps, low resource consumption, and favorable conditions for subsequent material applications. Furthermore, the functionalized silanes, siloxanes, or polysiloxanes obtained by this invention show promising industrial application prospects in the field of organosilicon functional materials.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] A method for preparing α-silyl sulfide functionalized silanes, siloxanes or polysiloxanes by iron catalysis involving sulfinates includes mixing a substrate (silane, siloxane or polysiloxane), a sulfinate compound, a catalyst, an additive and a solvent, and reacting them at 0 to 120°C for 1 to 48 hours under light irradiation.

[0009] The silane, siloxane, or polysiloxane substrate contains a C(sp) reaction-resistant material. 3 The α-silylalkyl site of the )-H functionalization reaction, wherein the sulfinate compound reacts with the α-silylalkyl site to form a CS bond on the substrate;

[0010] The structural formula of the sulfinate compound is: ;

[0011] R 3 The aryl group is selected from aryl, heteroaryl, or alkyl groups; the aryl group is phenyl, naphthyl, anthracel, or phenanthryl; the heteroaryl group is pyridyl, thiophene, oxazolyl, thiazolyl, imidazolyl, quinolinyl, furanyl, indolyl, or carbazoleyl; the alkyl group is a C1-C12 straight-chain or branched alkyl group, cyclopropane, cyclopentane, or cyclohexane; the aryl or heteroaryl group may optionally have 1 to 5 substituents, the substituents being selected from one or more of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyano, trifluoromethyl, alkoxy, phenyl, phenoxy, or ester, and the substituents are located in one or more of the ortho, meta, and para positions;

[0012] R 4 It is potassium or sodium.

[0013] Furthermore, when the substrate is a siloxane, the reaction is as follows: ;

[0014] Where R1 It is selected from one of the following groups: trimethylsilyl, dimethylsilyl, silylmethyl, methyl, ethyl, aryl.

[0015] Furthermore, when the substrate is a silane, the reaction is as follows: ;

[0016] Where R 2 It is selected from one of the following groups: trimethylsilyl, dimethylsilyl, silylmethyl, methyl, ethyl, ynyl, aryl.

[0017] Preferably, the catalyst is selected from one or more of ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferrocene, ferric acetylacetonate, tetrabutylammonium decatungstate, nickel chloride, cobalt chloride, copper chloride, chromium trichloride, or chromium dichloride;

[0018] The additive is selected from one or more of acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, trichloroacetyl chloride, p-methylbenzoyl chloride, p-chlorobenzoyl chloride, o-chlorobenzoyl chloride, methanesulfonyl chloride, potassium chloride, calcium chloride, magnesium chloride, zinc chloride, ferrous chloride, ferric chloride, tetramethylammonium chloride, tetrapropylammonium chloride, benzyltriethylammonium chloride, tetraphenylphosphine chloride, dimethylchlorosilane, methyldichlorosilane, phenyldimethylchlorosilane, diphenylchlorosilane, p-toluenesulfonyl chloride, benzoyl chloride, oxaloyl chloride, hydrochloric acid, lithium chloride, ammonium chloride, sodium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylchlorosilane, triethylchlorosilane, or tert-butyldimethylchlorosilane.

[0019] Preferably, the solvent is selected from one or more of acetonitrile, dichloromethane, acetone, tetrahydrofuran, toluene, ethyl acetate, methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide, or 1,4-dioxane.

[0020] Preferably, the number average molecular weight of the polysiloxane is 500-200,000, and the degree of polymerization of the oligosiloxane is 2-500.

[0021] Preferably, the illumination conditions are violet light, blue light, visible light, or ultraviolet light.

[0022] More preferably, the illumination condition is light irradiation with a wavelength of 300-500 nm, and the light is selected from one or more of violet light, ultraviolet light, and blue light.

[0023] Preferably, the amount of catalyst used is 1 to 150 mol% of the molar amount of sulfinate compound; the amount of additive used is 0.5 to 50 times the molar amount of sulfinate compound; and the molar ratio of substrate to sulfinate compound is 1:0.5 to 1:50.

[0024] This invention also claims protection for α-silicone-based sulfide functionalized silanes, siloxanes, or polysiloxanes prepared by the above preparation method.

[0025] This invention also claims protection for the use of α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes. Further, the functionalization rate of the sulfide functional group is 5% to 95%.

[0026] The aforementioned α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes can be used to prepare organosilicon functional materials, coating materials, surface modified materials, interface control materials, adhesives, pressure-sensitive adhesives, sealing materials, potting materials, electronic packaging materials, electrical insulating materials, dielectric materials, thermally conductive interface materials, flexible materials, flexible electronic materials, wearable materials, optical materials, optoelectronic functional materials, transparent packaging materials, biomedical materials, medical care materials, anti-corrosion materials, antifouling materials, waterproof and moisture-proof materials, weather-resistant materials, high and low temperature resistant materials, chemical corrosion resistant materials, flame-retardant materials, membrane materials, separation materials, filter materials, or sensing materials.

[0027] "Substitution" refers to the replacement of hydrogen atoms in a molecule by other different atoms or molecules.

[0028] The minimum and maximum carbon atom content in hydrocarbon groups are indicated by prefixes. For example, the prefix (Ca~Cb)alkyl indicates any alkyl group containing "a" to "b" carbon atoms. Therefore, for example, (C1~C4)alkyl refers to an alkyl group containing 1 to 4 carbon atoms.

[0029] The C1-C6 alkyl groups refer to alkyl groups of C1, C2, C3, C4, C5, and C6, that is, straight-chain or branched alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, hexyl, etc. The alkoxy groups of C1-C6 also have the corresponding meanings of their respective groups.

[0030] The aryl group is a carbon aryl group, representing C6–C. 20 Aromatic carbon rings, preferably phenyl or naphthyl;

[0031] Heteroaryl refers to a 5–20 membered aromatic heterocycle containing 1–3 N, O, or S heteroatoms, preferably pyridyl, pyrimidinyl, thiopheneyl, furanyl, imidazolyl, quinolinyl, etc.

[0032] Compared with the prior art, the beneficial effects of the present invention are:

[0033] (1) No pre-activation required for inert C(sp) 3 )-H bond: In this invention, the C(sp) bond is directly used on the alkyl group of silane, siloxane or polysiloxane. 3The -H bond is the reaction site, eliminating the need for prior halogenation, metallization, introduction of directing groups, or other activation treatments, thus shortening the synthetic route, simplifying the operation steps, and improving atom economy.

[0034] (2) The use of abundant metallic iron as catalyst results in lower cost and greater green chemistry sustainability: The catalytic system used in this invention uses iron salt as catalyst, which avoids dependence on precious metal catalysts such as palladium, rhodium, and iridium. It has the advantages of abundant source, low price, and low toxicity, which meet the requirements of green chemistry and sustainable development.

[0035] (3) Mild reaction conditions and simple operation: The present invention can realize the functionalization reaction of silane, siloxane or polysiloxane under light conditions without high temperature and high pressure conditions. The reaction can be carried out at room temperature or lower temperature. The operation is simple and the reaction conditions are relatively mild, which is conducive to reducing energy consumption and improving experimental operability.

[0036] (4) C–S bonds can be directly constructed at the alkyl sites of silanes, siloxanes or polysiloxanes: This invention uses sulfinate compounds as functionalizing agents to directly construct C–S bonds at the alkyl sites of silanes, siloxanes or polysiloxanes, thereby obtaining functionalized silanes, siloxanes or polysiloxanes, providing a new technical approach for the post-modification and structural diversification of organosilicon materials.

[0037] (5) Wide range of substrates: It can be applied to a variety of sulfinate compounds and different types of silanes, siloxanes or polysiloxanes, which is beneficial for preparing functional organosilicon compounds with diverse structures.

[0038] (6) A new technical means is provided for the post-functionalization of organosilicon compounds and their polymer materials: The present invention establishes a method for the direct functionalization of alkyl sites of silanes, siloxanes or polysiloxanes based on iron catalysis and light conditions, which provides a new method for the molecular design, subsequent structural modification and development of novel functional materials of organosilicon compounds. Attached Figure Description

[0039] Figure 1 This is the NMR characterization image of the polysiloxane functionalized product synthesized in Example 14 of the present invention.

[0040] Figure 2 The image shows the NMR characterization of the polysiloxane functionalized product synthesized in Example 15 of this invention. Detailed Implementation

[0041] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods used in the embodiments of the present invention are conventional methods; the materials and reagents used, unless otherwise specified, are commercially available reagents and materials.

[0042] Example 1: Functionalization reaction of sodium benzenesulfinate with hexamethyldisiloxane

[0043] Method: Sodium phenylsulfinate (0.4 mmol), ferric chloride (10 mol%, 0.02 mmol), acetonitrile (2 mL), acetyl chloride (0.5 mmol), and hexamethyldisiloxane (4.0 mmol) were added sequentially to the reaction flask. The system was then purged five times with argon gas. The reaction flask was placed at room temperature and irradiated with 390-400 nm ultraviolet light (the wavelength of ultraviolet light irradiation is the same as the wavelength here). The reaction was carried out for about 24 hours. After the reaction was completed, the product was purified to obtain the product with a yield of 88%.

[0044]

[0045] Yield: 88%

[0046] 1 H NMR (400 MHz, Chloroform- d )δ 7.30 – 7.20 (m, 4H), 7.11 – 7.05 (m,1H), 2.17 (s, 2H), 0.19 (s, 6H), 0.09 (s, 9H).

[0047] 13 C NMR (101 MHz, Chloroform- d )δ 140.32, 128.79, 126.26, 124.76,19.64, 2.05, 0.57.

[0048] Example 2: Functionalization reaction of sodium benzenesulfinate with hexamethyldisiloxane catalyzed by tetrabutylammonium decatungstate

[0049] The implementation method is the same as in Example 1.

[0050] Yield: 74%

[0051] Example 3: Functionalization reaction of sodium benzenesulfinate with hexamethyldisiloxane catalyzed by copper chloride

[0052] The implementation method is the same as in Example 1.

[0053] Yield: 41%

[0054] Example 4: Functionalization reaction of p-methyl-substituted aryl sulfinates with hexamethyldisiloxane

[0055] The implementation method is the same as in Example 1.

[0056] Yield: 86%

[0057] 1 H NMR (400 MHz, Chloroform-d) δ 7.21 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.2 Hz, 2H), 2.31 (s, 3H), 2.19 (s, 2H), 0.21 (s, 6H), 0.12 (s, 9H).

[0058] 13 C NMR (101 MHz, Chloroform-d) δ 136.67, 134.71, 129.59, 126.89, 21.03, 20.41, 2.05, 0.55.

[0059] Example 5: Functionalization reaction of p-fluorinated aryl sulfinates with hexamethyldisiloxane

[0060] The implementation method is the same as in Example 1.

[0061] Yield: 54%

[0062] 1 H NMR (400 MHz, Chloroform- d ) δ 7.35 – 7.19 (m, 2H), 6.98 (t, J=8.7 Hz, 2H), 2.18 (s, 2H), 0.21 (s, 6H), 0.11 (s, 9H).

[0063] 13 C NMR (101 MHz, Chloroform- d ) δ 162.29, 159.86, 135.28, 128.71,128.63, 115.98, 115.76, 21.11, 2.04, 0.54.

[0064] Example 6: Functionalization reaction of cyano-substituted aryl sulfinates with hexamethyldisiloxane

[0065] The implementation method is the same as in Example 1.

[0066] Yield: 91%

[0067] 1 H NMR (400 MHz, Chloroform-d)δ 7.52– 7.43 (m, 2H), 7.39– 7.30 (m,2H), 2.17 (s, 2H), 0.23 (s, 6H), 0.11 (s, 9H).

[0068] 13 C NMR (101 MHz, Chloroform-d) δ 142.94, 130.18, 129.18, 128.58,128.01, 118.76, 113.06, 19.20, 1.99, 0.57.

[0069] Example 7: Functionalization reaction of pyridyl sulfinate with hexamethyldisiloxane

[0070] The implementation method is the same as in Example 1.

[0071] Yield: 44%

[0072] 1 H NMR (400 MHz, Chloroform- d ) δ 7.37 (d, J = 8.6 Hz, 2H), 7.14 (d, J= 8.6 Hz, 2H), 2.15 (s, 2H), 0.21 (s, 6H), 0.11 (s, 6H), 0.07 (s, 6H).

[0073] 13 C NMR (101 MHz, Chloroform- d ) δ 139.71, 131.73, 127.79, 118.24,19.81, 14.27, 2.03, 1.17, 0.58.

[0074] Example 8: Functionalization reaction of thienylsulfinate with hexamethyldisiloxane

[0075] The implementation method is the same as in Example 1.

[0076] Yield: 62%

[0077] 1 H NMR (400 MHz, Chloroform- d ) δ 7.25 (d, J = 1.2 Hz, 1H), 7.04 (dd, J = 3.6, 1.2 Hz, 1H), 6.94 (dd, J = 5.3, 3.6 Hz, 1H), 2.29 (s, 2H), 0.18 (s, 6H), 0.11 (s, 9H).

[0078] 13 C NMR (101 MHz, Chloroform- d ) δ 139.88, 129.90, 127.48, 127.23,26.99, 2.04, 0.42.

[0079] Example 9: Functionalization reaction of oxazolyl sulfinate with hexamethyldisiloxane

[0080] The implementation method is the same as in Example 1.

[0081] Yield: 66%

[0082] 1 H NMR (400 MHz, Chloroform-d ) δ 2.43 (s, 3H), 2.30 (s, 3H), 1.91 (s, 2H), 0.18 (s, 6H), 0.10 (s, 9H).

[0083] 13 C NMR (101 MHz, Chloroform- d )δ 171.12, 162.15, 109.79, 23.76, 11.59,10.49, 2.00, 0.25.

[0084] Example 10: Functionalization reaction of cyclopropyl sulfinate with hexamethyldisiloxane

[0085] The implementation method is the same as in Example 1.

[0086] Yield: 69%

[0087] 1 H NMR (400 MHz, Chloroform- d ) δ 1.89 (s, 2H), 0.80 (td, J = 6.4, 4.4Hz, 2H), 0.52 (dt, J = 6.1, 4.2 Hz, 2H), 0.14 (s, 6H), 0.09 (s, 9H).

[0088] 13 C NMR (101 MHz, Chloroform- d ) δ 19.02, 14.38, 6.73, 0.12, -1.50.

[0089] Example 11: Functionalization reaction of sodium benzenesulfinate with cyclotetrasiloxane

[0090] The implementation method is the same as in Example 1.

[0091] Yield: 58%

[0092] 1 H NMR (400 MHz, Chloroform- d) δ 7.32 – 7.22 (m, 4H), 7.14 – 7.06 (m,1H), 2.20 (s, 2H), 0.25 (s, 3H), 0.15 (s, 6H), 0.13 (s, 9H), 0.11 (s, 3H).

[0093] 13 C NMR (101 MHz, Chloroform- d ) δ 140.09, 128.80, 126.44, 124.84,18.53, 0.93, 0.91, 0.88, 0.86, 0.83, -0.71.

[0094] Example 12: Functionalization reaction of sodium benzenesulfinate with alkynylsilane

[0095] The implementation method is the same as in Example 1.

[0096] Yield: 64%

[0097] 1 H NMR (400 MHz, Chloroform- d ) δ 7.33 – 7.24 (m, 4H), 7.15 – 7.09 (m,1H), 2.30 (s, 2H), 0.30 (s, 6H), 0.19 (s, 9H).

[0098] 13 C NMR (101 MHz, Chloroform- d ) δ 139.90, 128.84, 126.73, 125.05,18.11, -0.02, -1.66.

[0099] Example 13: Functionalization reaction of sodium benzenesulfinate with linear disilane

[0100] The implementation method is the same as in Example 1.

[0101] Yield: 61%

[0102] 1 H NMR (400 MHz, Chloroform- d) δ 7.30 – 7.23 (m, 4H), 7.10 (dp, J =6.8, 1.9 Hz, 1H), 2.17 (s, 2H), 0.19 (s, 6H), 0.07 (s, 9H), -0.08 (s, 2H).

[0103] 13 C NMR (101 MHz, Chloroform- d ) δ 140.57, 128.79, 126.15, 124.71,19.54, 2.77, 1.47, -0.39.

[0104] Example 14

[0105] Procedure: Sodium phenylsulfinate (0.4 mmol), ferric chloride (10 mol%, 0.02 mmol), acetonitrile (2 mL), acetyl chloride (0.5 mmol), and polysiloxane (2.0 mmol) were added sequentially to the reaction flask. The system was then purged five times with argon gas. The reaction flask was placed at room temperature and irradiated with ultraviolet light. After the reaction was complete, the product was purified to obtain a functionalization of 8.5%. Figure 1 As shown, the functionalization degree of the compound prepared by it is calculated to be 8.5%.

[0106]

[0107] Example 15

[0108] The implementation method is the same as in Example 12, such as... Figure 2 As shown, the functionalization degree of the compound prepared by it was calculated to be 12.8%.

[0109]

[0110] Obviously, the specific implementation schemes described above are merely a further detailed explanation of the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above descriptions are only specific examples of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes involving iron-catalyzed sulfinates, characterized in that, This involves mixing a substrate, a sulfinate compound, a catalyst, an additive, and a solvent, and reacting them under light conditions at 0–120°C for 1–48 hours. The substrate is a silane, siloxane, or polysiloxane, wherein the silane, siloxane, or polysiloxane substrate contains a component capable of undergoing C(sp) oxidation. 3 The α-silylalkyl site of the )-H functionalization reaction, wherein the sulfinate compound reacts with the α-silylalkyl site to form a CS bond on the substrate; The structural formula of the sulfinate compound is: ; R 3 The aryl group is selected from aryl, heteroaryl, or alkyl groups; the aryl group is phenyl, naphthyl, anthracel, or phenanthryl; the heteroaryl group is pyridyl, thiophene, oxazolyl, thiazolyl, imidazolyl, quinolinyl, furanyl, indolyl, or carbazoleyl; the alkyl group is a C1-C12 straight-chain or branched alkyl group, cyclopropane, cyclopentane, or cyclohexane; the aryl or heteroaryl group may optionally have 1 to 5 substituents, the substituents being selected from one or more of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyano, trifluoromethyl, alkoxy, phenyl, phenoxy, or ester, and the substituents are located in one or more of the ortho, meta, and para positions; R 4 It is potassium or sodium.

2. The method for preparing α-silicone-based sulfonate-functionalized silanes, siloxanes, or polysiloxanes catalyzed by iron sulfinate according to claim 1, characterized in that, When the substrate is a siloxane, the structural formula of the siloxane is: ;where R 1 Selected from one of the following groups: trimethylsilyl, dimethylsilyl, silylmethyl, methyl, ethyl, aryl; when R in the siloxane structural formula 1 When selected from aryl, the aryl group is phenyl, naphthyl, anthraceneyl, or phenanthrene.

3. The method for preparing α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes involving iron catalysis and sulfinate as described in claim 1, characterized in that, When the substrate is silane, the structural formula of silane is: ;where R 2 Selected from one of the following groups: trimethylsilyl, dimethylsilyl, silylmethyl, methyl, ethyl, ynyl, aryl; when R in the silane structural formula 2 When selected from aryl, the aryl group is phenyl, naphthyl, anthraceneyl, or phenanthrene.

4. The method for preparing α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes involving iron catalysis and sulfinate as described in claim 1 or 2, characterized in that, The catalyst is selected from one or more of the following: ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric sulfate, ferrous sulfate, ferrous nitrate, ferrous nitrate, ferrocene, ferric acetylacetonate, tetrabutylammonium decatungstate, nickel chloride, cobalt chloride, copper chloride, chromium trichloride, or chromium dichloride. The additive is selected from one or more of acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, trichloroacetyl chloride, p-methylbenzoyl chloride, p-chlorobenzoyl chloride, o-chlorobenzoyl chloride, methanesulfonyl chloride, potassium chloride, calcium chloride, magnesium chloride, zinc chloride, ferrous chloride, ferric chloride, tetramethylammonium chloride, tetrapropylammonium chloride, benzyltriethylammonium chloride, tetraphenylphosphine chloride, dimethylchlorosilane, methyldichlorosilane, phenyldimethylchlorosilane, diphenylchlorosilane, p-toluenesulfonyl chloride, benzoyl chloride, oxaloyl chloride, hydrochloric acid, lithium chloride, ammonium chloride, sodium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylchlorosilane, triethylchlorosilane, or tert-butyldimethylchlorosilane.

5. The method for preparing α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes involving iron catalysis and sulfinate as described in claim 1, characterized in that, The solvent is selected from one or more of acetonitrile, dichloromethane, acetone, tetrahydrofuran, toluene, ethyl acetate, methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide, or 1,4-dioxane.

6. The method for preparing α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes involving iron catalysis and sulfinate according to claim 1, characterized in that, The substrate is selected from one or more of cyclic siloxanes, linear siloxanes, oligomeric siloxanes, or polysiloxanes; the number average molecular weight of the polysiloxane is 500 to 200,000, and the degree of polymerization of the oligomeric siloxane is 2 to 500.

7. The method for preparing α-silyl sulfide functionalized silanes, siloxanes, or polysiloxanes involving iron catalysis and sulfinate according to claim 1, characterized in that, The illumination conditions are violet light, blue light, or ultraviolet light.

8. The preparation method according to claim 1, characterized in that, The amount of catalyst used is 1 to 150 mol of the molar amount of sulfinate compound; the amount of additive used is 0.5 to 50 times the molar amount of sulfinate compound; the molar ratio of substrate to sulfinate compound is 1:0.5 to 1:

50.

9. The application of the preparation method according to claim 1 in the preparation of α-silicone sulfide functionalized silanes, siloxanes, or polysiloxanes, characterized in that, The functionalization rate of the sulfide functional group is 5% to 95%.

10. The application according to claim 9, characterized in that, The α-silyl sulfide functionalized silane, siloxane, or polysiloxane is used to prepare coatings, surface modifications, adhesive seals, electronic packaging, flexible, biomedical, membrane separation, or sensing materials.

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