Method for preparing organic multi-sulfur polymer through photoreaction of sulfur and polyhalide at room temperature
Organic polysulfide polymers were prepared at room temperature using a visible light-induced photoreaction method with polyhalogenated compounds and elemental sulfur. This method solves the problems of monomer miscibility and reactivity differences in traditional methods, expands the types of raw materials, and realizes efficient and environmentally friendly polymer synthesis, which can be applied to photocatalysis and heavy metal adsorption.
Patent Information
- Application Number
- CN202410750665.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-12
- Publication Date
- 2025-12-16
AI Technical Summary
Existing technologies for synthesizing organic polysulfide polymers suffer from insufficient monomer miscibility, inhomogeneity due to differences in reactivity, and self-acceleration. Furthermore, traditional methods require substrates containing unsaturated double or triple bonds, which limits the types of raw materials and reaction conditions.
An organic polysulfide polymer was prepared at room temperature by using a visible light-induced photoreaction method, in which polyhalogenated compounds and elemental sulfur reacted under an inert gas atmosphere. The reaction was carried out by the photoreaction of sulfur with polyhalogenated compounds. The reducing agents used were triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene and the solvents were N,N-dimethylacetamide. The photoreaction time was 24-48 hours.
The range of raw materials has been expanded, enabling the mild and efficient synthesis of organic polysulfide polymers. The operation is simple, with low environmental pollution and high conversion rate. The prepared polymers can be used for photocatalysis and heavy metal adsorption.
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Figure CN121136084A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials chemistry, and specifically relates to a method for preparing organic polysulfide polymers by photoreaction of sulfur with polyhalogenated compounds at room temperature. Background Technology
[0002] In the interdisciplinary field of chemistry and materials science, the synthesis and application of organic polysulfide polymers have always attracted much attention. However, traditional synthesis methods have many unresolved problems. On the one hand, insufficient miscibility between monomers or differences in their reactivity under high-temperature conditions may lead to heterogeneity in the final synthesized polymer, thus affecting its properties. On the other hand, uncontrollable self-acceleration phenomena may occur during polymerization, which undoubtedly increases the uncertainty and technical difficulty of the preparation process. Therefore, exploring a mild, efficient, and environmentally friendly method for synthesizing organic polysulfide polymers has become a current research hotspot.
[0003] In 2019, Hasell et al. reported the catalytic effects of metal salts, metal oxides, and metal complexes on reverse sulfidation reactions. This catalytic method effectively reduced the required reaction temperature and time for most monomers, prevented harmful H2S generation, increased yields, and allowed the use of monomers that would otherwise not react. In 2021, Hasell et al. reported the establishment and exploration of a reverse sulfidation catalyst library, studying three classes of catalysts and up to 32 compounds and their combinations, and making some preliminary inferences about the reaction mechanism through experiments with these catalysts. In 2022, Hasell et al. reported a mechanochemical synthetic route (mechanical milling) for reverse sulfidation, which has advantages such as mild conditions (room temperature), short reaction time (3 h), high atom economy, less hydrogen sulfide production, and a wider range of monomers. Polymers can be successfully obtained from aromatic, aliphatic, and volatile monomers, including renewable monomers, demonstrating the effectiveness and versatility of this method. In the same year, Pyun et al. reported a polymerization method using the inexpensive petrochemical product S2Cl2 instead of elemental sulfur for crosslinking. By reacting the highly reactive S2Cl2 with various allyl-containing monomers at 50-70 °C, soluble, high-molar-mass linear polymers, block copolymers, and crosslinked thermosetting polymers can be prepared. Also in the same year, Hasell et al. reported the generation of polymers through visible-light photocatalysis, allowing the reaction to proceed at room temperature and significantly expanding the range of substrates and products. These conditions enable the use of volatile gaseous olefins and alkynes for reverse vulcanization.
[0004] While the methods described above operate under mild conditions, they all require unsaturated double or triple bonds in the substrate structure, and examples using saturated organic compounds as monomers have not yet been reported. Therefore, this invention develops a novel strategy for synthesizing organic polysulfide polymers using visible light-induced synthesis from haloalkanes and elemental sulfur. This strategy enables efficient synthesis of organic polysulfide polymers under mild conditions, providing new ideas and solutions for the green synthesis of organic polysulfide polymers. Summary of the Invention
[0005] The purpose of this invention is to provide a method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated compounds.
[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing organic polysulfide polymers by photoreaction of sulfur with polyhalogenated compounds at room temperature involves mixing polyhalogenated compounds, S8 solid, reducing agent and solvent under inert gas as a protective gas, and then carrying out the photoreaction at room temperature to obtain organic polysulfide polymers.
[0007] Furthermore, the polyhalogenated product comprises any one of the following structural formulas: .
[0008] Further, the reducing agent is any one of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and N,N-diisopropylethylamine (DIPEA).
[0009] Furthermore, the solvent is N , N -Any of dimethylacetamide (DMAC), methanol, and acetonitrile.
[0010] Furthermore, the molar ratio of the polyhalogenated product to the S8 solid is 1:0.25-6.
[0011] Furthermore, the molar ratio of the reducing agent to the S8 solid is 2-20:1.
[0012] Furthermore, the ratio of S8 solid to solvent is 5-120 mg / mL.
[0013] Furthermore, the photoreaction uses light with a wavelength range of 400-525 nm.
[0014] Furthermore, the photoreaction time is 24-48 h.
[0015] The organic polysulfide polymers prepared by the above method can be used as photocatalysts for visible light-catalyzed organic reactions.
[0016] Furthermore, the organic reaction is specifically a cross-coupling reaction of free radicals.
[0017] The organic polysulfide polymers prepared by the above method can also be used for the adsorption of heavy metals.
[0018] Furthermore, the heavy metal ions are one or more of Hg(II), Pd(II), Au(III), Pb(II), and Ag(I).
[0019] The present invention has the following advantages over the prior art: (1) This invention expands the range of raw materials used to synthesize organic polysulfide polymers.
[0020] (2) The preparation method of the present invention is simple to operate, mild in conditions, low in environmental pollution and high in conversion rate. Attached Figure Description
[0021] Figure 1 shows the FT-IR spectrum of the organic polysulfide polymer prepared in Example 1.
[0022] Figure 2 shows the FT-IR spectrum of the organic polysulfide polymer prepared in Example 54.
[0023] Figure 3 shows the X-ray powder diffraction patterns of the organic polysulfide polymers prepared in some of the embodiments.
[0024] Figure 4 shows the Pb obtained in application example 2. 2+ Ion adsorption curve. Detailed Implementation
[0025] A method for preparing organic polysulfide polymers by photoreaction of sulfur with polyhalogenated compounds at room temperature involves adding polyhalogenated compounds and S8 solid at a molar ratio of 1:0.25-6 into a Schlenk reaction tube under inert gas as a protective gas, adding a reducing agent and solvent, mixing, and reacting at room temperature under 400-525 nm light irradiation for 24-48 h to obtain organic polysulfide polymers.
[0026] The polyhalogenated derivatives used include any one of the following structural formulas: .
[0027] The reducing agent used is any one of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or N,N-diisopropylethylamine (DIPEA).
[0028] The solvent used is N , N -Any of dimethylacetamide (DMAc), methanol, and acetonitrile.
[0029] The molar ratio of the reducing agent to S8 solid is 2-20:1.
[0030] The ratio of S8 solid to solvent is 5-120 mg / mL.
[0031] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.
[0032] Example 1 Weigh 29.7 mg of 1,2-dichloroethane (1a), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0033] Example 2 Weigh 56.4 mg of 1,2-dibromoethane (1b), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0034] Example 3 Weigh 84.6 mg of 1,2-diiodoethane (1c), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0035] Example 4 Weigh 33.9 mg of 1,3-dichloro-2-propanol (1d), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0036] Example 5 Weigh 60.6 mg of 1,3-dibromo-2-propanol (1e), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0037] Example 6 Weigh 88.8 mg of 1,3-diiodo-2-propanol (1f), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0038] Example 7 Weigh 38.7 mg of 1,2-dichloropropane (1 g), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0039] Example 8 Weigh 38.7 mg of 2,3-dichloro-1-propanol (1 h), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0040] Example 9 Weigh 44.2 mg of 1,2,3-trichloropropane (1i), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0041] Example 10 Weigh 33.9 mg of 1,3-dichloropropane (1j), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0042] Example 11 Weigh 60.6 mg of 1,3-dibromopropane (1k), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 425 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0043] Example 12 Weigh 88.8 mg of 1,3-diiodopropane (1 L), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 425 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0044] Example 13 Weigh 37.5 mg of 3-chloro-2-chloromethyl-1-propene (1m), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 425 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0045] Example 14 Weigh 38.1 mg of 3-chloropropionyl chloride (1n), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 425 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0046] Example 15 Weigh 57.4 mg of 3-chloro-2,2-di(chloromethyl)-1-propanol (1o), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 425 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0047] Example 16 Weigh 33.9 mg of chloroacetyl chloride (1p), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 36 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0048] Example 17 Weigh 37.2 mg of 2,3-dichloropropionitrile (1q), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 36 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0049] Example 18 Weigh 38.1 mg of 2-methyl-1,2-dichloropropane (1r), 122.9 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 36 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0050] Example 19 Weigh 38.1 mg of 1,4-dichlorobutane (1s), 163.8 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 36 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0051] Example 20 Weigh 64.8 mg of 1,4-dibromobutane (1 t), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 36 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0052] Example 21 Weigh 93.0 mg of 1,4-diiodobutane (1u), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 500 nm green light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0053] Example 22 Weigh 69.0 mg of 1,4-dibromopentane (1 v), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 500 nm green light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0054] Example 23 Weigh 82.2 mg of methyl 2,5-dibromopentanoate (1 w), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 500 nm green light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0055] Example 24 Weigh 74.4 mg of 1,4-dibromo-2,3-butanediol (1x), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 500 nm green light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0056] Example 25 Weigh 73.2 mg of 2,5-dibromohexane (1y), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 500 nm green light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0057] Example 26 Weigh 42.3 mg of 1,5-dichloropentane (1z), 38.5 mg of S8 powder, 193.9 mg of triethylamine and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0058] Example 27 Weigh 69.0 mg of 1,5-dibromopentane (1aa), 38.5 mg of S8 powder, 193.9 mg of triethylamine and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0059] Example 28 Weigh 97.2 mg of 1,5-diiodopentane (1ab), 38.5 mg of S8 powder, 193.9 mg of triethylamine and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0060] Example 29 Weigh 46.5 mg of 5-chloropentanoyl chloride (1ac), 38.5 mg of S8 powder, 193.9 mg of triethylamine and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0061] Example 30 Weigh 50.7 mg of glutaryl chloride (1ad), 38.5 mg of S8 powder, 193.9 mg of triethylamine and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0062] Example 31 Weigh 73.2 mg of 1,5-dibromo-3-methylpentane (1ae), 122.9 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of DMAc into a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0063] Example 32 Weigh 46.5 mg of 1,6-dichlorohexane (1af), 163.8 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of DMAc into a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is complete, filter and dry to obtain the corresponding organic polysulfide polymer.
[0064] Example 33 Weigh 73.2 mg of 1,6-dibromohexane (1 ag), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of DMAc into a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is complete, filter and dry to obtain the corresponding organic polysulfide polymer.
[0065] Example 34 Weigh 101.4 mg of 1,6-diiodohexane (1ah), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of DMAc into a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0066] Example 35 Weigh 54.9 mg of adipic acid chloride (Ia), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of DMAc and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0067] Example 36 Weigh 60.3 mg of 1,3-dichloro-2-(acetoxymethoxy)propane (1aj), 38.5 mg of S8 powder, 193.9 mg of DBU and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0068] Example 37 Weigh 91.2 mg of 2,5-dibromoadipic acid (1ak), 38.5 mg of S8 powder, 193.9 mg of DBU and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0069] Example 38 99.6 mg of dimethyl 2,5-dibromoadipate (1a1), 38.5 mg of S8 powder, 193.9 mg of DBU and 3 mL of MeCN were weighed and added to a Schlenk reaction tube. The reaction was carried out under inert gas protection at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0070] Example 39 108.0 mg of diethyl 2,5-dibromoadipate (1 am), 38.5 mg of S8 powder, 193.9 mg of DBU and 3 mL of MeCN were weighed and added to a Schlenk reaction tube. The reaction was carried out under inert gas protection at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0071] Example 40 Weigh 56.13 mg of 1,2-bis(2-chloroethoxy)ethane (Ian), 38.5 mg of S8 powder, 193.9 mg of DBU and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0072] Example 41 Weigh 82.8 mg of 1,2-bis(2-bromoethoxy)ethane (1ao), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0073] Example 42 111.0 mg of 1,2-bis(2-iodoethoxy)ethane (1ap), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN were weighed and added to a Schlenk reaction tube. The reaction was carried out under inert gas protection at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0074] Example 43 Weigh 52.5 mg of 1,4-dichlorobenzyl (1aq), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0075] Example 44 Weigh 79.2 mg of 1,4-dibenzyl bromide (1ar), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0076] Example 45 Weigh 107.4 mg of 1,4-dibenzyl iodine (1as), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0077] Example 46 Weigh 75.3 mg of 4,4'-di(chloromethyl)biphenyl (1 at), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0078] Example 47 Weigh 102.0 mg of 4,4'-di(bromomethyl)biphenyl (1au), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0079] Example 48 Weigh 130.2 mg of 4,4'-bis(iodomethyl)biphenyl (1av), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, react at room temperature and under 450 nm blue light irradiation for 48 h. After the reaction is completed, filter and dry to obtain the corresponding organic polysulfide polymer.
[0080] Example 49 Weigh 82.6 mg of 9,10-dichloromethylanthracene (1aw), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0081] Example 50 Weigh 79.6 mg of 4,4'-di(chloromethyl)diphenylmethane (1ax), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction was carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0082] Example 51 106.2 mg of 4,4'-bis(bromomethyl)diphenylmethane (Iay), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN were weighed and added to a Schlenk reaction tube. The reaction was carried out under inert gas protection at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0083] Example 52 Weigh 67.1 mg of 1,3,5-tris(chloromethyl)benzene (1az), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0084] Example 53 Weigh 79.7 mg of 1,3,5-trimethyl-2,4,6-trichloromethylbenzene (1aaa), 38.5 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0085] Example 54 95.8 mg of hexabutyltribenzyl bromide (1aab), 122.9 mg of S8 powder, 193.9 mg of DIPEA and 3 mL of MeCN were weighed and added to a Schlenk reaction tube. The reaction was carried out under inert gas protection at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction was completed, the mixture was filtered and dried to obtain the corresponding organic polysulfide polymer.
[0086] Example 55 Weigh 51.4 mg of tetraphenylmethane tetrabenzyl chloride (1aac), 123.8 mg of S8 powder, 258.8 mg of DIPEA and 3 mL of MeCN and add them to a Schlenk reaction tube. Under inert gas protection, the reaction is carried out at room temperature and irradiated with 450 nm blue light for 48 h. After the reaction is completed, the mixture is filtered and dried to obtain the corresponding organic polysulfide polymer.
[0087] Application Example 1: Visible light-catalyzed aryl radical cross-coupling reaction
[0088] Accurately weigh aromatic base compound 4a (39.8 mg, 0.2 mmol), N 5-Methylpyrrole 5a (355 mg, 4.0 mmol), H2O (7.2 mg, 0.4 mmol), IVP-EAE (10.0 mg), K2CO3 (41.5 mg, 0.3 mmol), and DMSO (1.0 mL) were added to a 10 mL Schlenk reaction tube, along with 10 mg of the organic polysulfide polymer prepared in the previous example as a photocatalyst. The reaction system was then subjected to three cycles of cryogenic degassing. After complete degassing, the reaction tube was sealed and placed 2-3 cm in front of a 30 W blue LED lamp. The mixture was stirred at room temperature and monitored in real-time using TLC until the reaction was complete. Water was added to terminate the reaction, followed by three extractions with EA. The organic phases were combined. The organic phase was concentrated under reduced pressure, and dibromomethane (0.2 mmol) was added. The NMR yield was calculated by calibration of the reaction mixture using coarse NMR, and the results are shown in Table 1.
[0089] Table 1 ,
[0090] As shown in Table 1, the different organic polysulfide polymers obtained in the examples can all be used as photocatalysts to ensure the smooth progress of the reaction, with yields ranging from 19% to 86%.
[0091] Application Example 2: Pb 2+ Ion adsorption First, prepare a series of Pb solutions with different concentrations. 2+ Ionic solution, then in 20 mL of Pb 2+ 20 mg of the organic polysulfide polymer prepared in Example 1 was added to an ionic solution, mixed thoroughly, and stirred at room temperature for 12 h. The effect of the organic polysulfide polymer on different concentrations of Pb was then tested. 2+ The adsorption of ion solutions was studied, and Langmuir curves were plotted using Origin software. The adsorption of Pb by the organic polysulfide polymer was then calculated. 2+ The adsorption capacity of ions is shown in the results. Figure 4 The fitting results show that the organic polysulfide polymer prepared in Example 1 is effective against Pb. 2+ The maximum adsorption value of the ions is 62.46 mg / g.
[0092] Application Example 3: Hg 2+ Ion adsorption First, prepare a series of Hg solutions with different concentrations. 2+ Ionic solution, then in 20 mL of Hg 2+ 20 mg of the organic polysulfide polymer prepared in Example 1 was added to an ionic solution, mixed thoroughly, and stirred at room temperature for 12 h. The effect of the organic polysulfide polymer on different concentrations of Hg was then tested. 2+ The adsorption of ion solutions was studied, and Langmuir curves were plotted using Origin software. The adsorption of Hg by the organic polysulfide polymer was then calculated. 2+ Adsorption capacity of ions. The fitting results show that the organic polysulfide polymer prepared in Example 1 has a high adsorption capacity for Hg. 2+ The maximum adsorption value of the ions is 314 mg / g.
[0093] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.
Claims
1. A method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated derivatives, characterized in that, Under the protection of an inert gas, a polyhalogenated compound, S8 solid, a reducing agent, and a solvent are mixed and subjected to a photo-reaction at room temperature to obtain an organic polysulfide polymer.
2. The method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated compounds according to claim 1, characterized in that: The polyhalogenated product includes any one of the following structural formulas: 。 3. The method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated compounds according to claim 1, characterized in that: The reducing agent is any one of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-diisopropylethylamine.
4. The method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated compounds according to claim 1, characterized in that: The solvent is N , N - Any one of dimethylacetamide, methanol, and acetonitrile.
5. The method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated compounds according to claim 1, characterized in that: The molar ratio of the polyhalogenated product to solid S8 is 1:0.25-6, the molar ratio of the reducing agent to solid S8 is 2-20:1, and the ratio of solid S8 to solvent is 5-120 mg / mL.
6. The method for preparing organic polysulfide polymers at room temperature via the photoreaction of sulfur with polyhalogenated compounds according to claim 1, characterized in that: The photoreaction uses light with a wavelength range of 400-525 nm and a reaction time of 24-48 h.
7. The application of an organic polysulfide polymer prepared by the method described in claim 1 in visible light photocatalytic organic reactions.
8. The application according to claim 7, characterized in that, The organic polysulfide polymer was used as a photocatalyst for the cross-coupling reaction of free radicals.
9. The application of an organic polysulfide polymer prepared by the method described in claim 1 in the adsorption of heavy metals.
10. The application according to claim 9, characterized in that, The heavy metal ions are one or more of Hg (II), Pd (II), Au (III), Pb (II), and Ag (I).