CN110801859B - Guanidyl modified mesoporous molecular sieve, and preparation method and application thereof - Google Patents

Guanidyl modified mesoporous molecular sieve, and preparation method and application thereof Download PDF

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CN110801859B
CN110801859B CN201911100739.9A CN201911100739A CN110801859B CN 110801859 B CN110801859 B CN 110801859B CN 201911100739 A CN201911100739 A CN 201911100739A CN 110801859 B CN110801859 B CN 110801859B
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molecular sieve
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费潇瑶
梁万根
张超
崔卫华
孙志利
靖培培
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Yifeng New Material Co.,Ltd.
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Shandong Efirm Biochemistry and Environmental Protection Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract

The invention provides a preparation method of a guanidyl modified mesoporous molecular sieve, which comprises the following steps: s1) performing amino functionalization on the surface of the mesoporous molecular sieve by using an amino-containing silane coupling agent to obtain an amino-functionalized mesoporous molecular sieve; s2) reacting the amino functionalized mesoporous molecular sieve with cyanamide to obtain the guanidyl modified mesoporous molecular sieve. Compared with the prior art, the preparation method of the guanidino modified mesoporous molecular sieve is simple, the guanidino modified mesoporous molecular sieve can be used for preparing the mercaptan compound through catalysis, the conversion rate and the purity of the mercaptan compound generated in the reaction process can be effectively improved, the catalyst can be recycled, the reaction period can be effectively shortened, the content of impurities in the synthesized thioether type cyclic sulfur compound is low, and the industrial application prospect is good.

Description

Guanidyl modified mesoporous molecular sieve, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a guanidyl modified mesoporous molecular sieve, and a preparation method and application thereof.
Background
In recent years, plastic lenses have been rapidly popularized in the fields of spectacle lenses, cameras, camera lenses, and the like, instead of conventional inorganic glass lenses, because of their advantages such as light weight, difficulty in breaking, and dyeability. At present, plastic lenses with low refractive index such as PC, PMMA, CR-39 and the like are generally used in the market, while plastic lenses with medium and high refractive index (refractive index of 1.60 and above) are more and more accepted by the public due to the characteristics of high light transmittance, ultraviolet resistance, ultra-thin and the like, but at present, most of the raw materials of optical resin lenses with refractive index of 1.60 and above in China depend on import. Therefore, resins used for plastic lenses are also required to have higher performance, including high refractive index, high abbe number, low specific gravity, high heat resistance, and the like.
At present, in addition to polythiourethane materials (Chinese patent with publication number CN101511895 Bde) which take polyisocyanate and polythiol as raw materials, resins synthesized by taking thioether type ring sulfur compounds as monomers have high refractive index and high Abbe number (Chinese patent with publication number CN106232658A and patent with patent number WO2010131631A 1) which are also very concerned by domestic markets, the refractive index of the resins can reach more than 1.70, and the requirements of people with high myopia degrees on the material and the performance of glasses can be met.
For the synthesis of episulfide compounds, which are monomer raw materials of thioether resins, the main synthesis process at present uses epichlorohydrin and a vulcanizing agent as raw materials, and the synthesis is carried out under alkaline conditions, a solvent is required in the process, the requirements on the purification and separation of intermediate products are high, and although a good episulfide compound monomer can be obtained, the synthesis is not beneficial to the preparation of higher-quality products (patent No. WO2011105319A 1).
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a guanidino modified mesoporous molecular sieve, a preparation method and an application thereof, wherein the guanidino modified mesoporous molecular sieve prepared by the method has a high catalytic activity when used as a catalyst for preparing a thiol compound.
The invention provides a preparation method of a guanidyl modified mesoporous molecular sieve, which comprises the following steps:
s1) performing amino functionalization on the surface of the mesoporous molecular sieve by using an amino-containing silane coupling agent to obtain an amino-functionalized mesoporous molecular sieve;
s2) reacting the amino functionalized mesoporous molecular sieve with cyanamide to obtain the guanidyl modified mesoporous molecular sieve.
Preferably, the silane coupling agent containing amino groups is selected from 3-aminopropyltriethoxysilane and/or 3-aminopropyltrimethoxysilane; the mesoporous molecular sieve is selected from one or more of SBA-15, MCM-41 and MCM-48.
Preferably, the mass ratio of the amino-containing silane coupling agent to the mesoporous molecular sieve is (0.5-4): 1.
preferably, the step S1) is specifically:
under the protective atmosphere, carrying out reflux reaction on an amino-containing silane coupling agent and a mesoporous molecular sieve in an organic solvent to obtain an amino-functionalized mesoporous molecular sieve; the time of the reflux reaction is 20-24 h.
Preferably, the molar ratio of the primary amino group to the cyanamide on the amino-functionalized mesoporous molecular sieve is (0.5-2): 1.
preferably, the temperature of the reaction in the step S2) is 50-120 ℃; the reaction time is 1-10 h.
The invention also provides a guanidyl modified mesoporous molecular sieve prepared by the method.
The invention also provides application of the guanidine-based modified mesoporous molecular sieve prepared by the method in preparation of a mercaptan compound catalyst.
The invention also provides a preparation method of the thioether-type episulfide compound, which comprises the following steps:
A1) reacting epoxy chloropropane with a first vulcanizing agent in the presence of the guanidine-modified mesoporous molecular sieve prepared by the method to obtain a thiol compound;
A2) reacting the thiol compound under alkaline conditions to obtain a thioether epoxy compound;
A3) and reacting the thioether epoxy compound with a second sulfur reagent to obtain the thioether epoxy sulfur compound.
The invention also provides the method, wherein the mass of the catalyst is 0.05-10% of that of epichlorohydrin. .
The invention provides a preparation method of a guanidyl modified mesoporous molecular sieve, which comprises the following steps: s1) performing amino functionalization on the surface of the mesoporous molecular sieve by using an amino-containing silane coupling agent to obtain an amino-functionalized mesoporous molecular sieve; s2) reacting the amino functionalized mesoporous molecular sieve with cyanamide to obtain the guanidyl modified mesoporous molecular sieve. Compared with the prior art, the preparation method of the guanidino modified mesoporous molecular sieve is simple, the guanidino modified mesoporous molecular sieve can be used for preparing the mercaptan compound through catalysis, the conversion rate and the purity of the mercaptan compound generated in the reaction process can be effectively improved, the catalyst can be recycled, the reaction period can be effectively shortened, the content of impurities in the synthesized thioether type cyclic sulfur compound is low, and the industrial application prospect is good.
Drawings
FIG. 1 shows the IR absorption spectra of SBA-15 and G/SBA-15 obtained in example 1 of the present invention;
FIG. 2 is a graph showing the activity change trend of G/SBA-15 obtained in example 1 after 20 times of recycling.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a guanidyl modified mesoporous molecular sieve, which comprises the following steps: s1) performing amino functionalization on the surface of the mesoporous molecular sieve by using an amino-containing silane coupling agent to obtain an amino-functionalized mesoporous molecular sieve; s2) reacting the amino functionalized mesoporous molecular sieve with cyanamide to obtain the guanidyl modified mesoporous molecular sieve.
In the present invention, the sources of all raw materials are not particularly limited, and the raw materials may be commercially available or self-made.
The amino-containing silane coupling agent is preferably 3-aminopropyltriethoxysilane and/or 3-aminopropyltrimethoxysilane, the mesoporous molecular sieve is preferably one or more of SBA-15, MCM-41 and MCM-48, more preferably SBA-15, the SBA-15 is preferably prepared by using a template agent poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (P123), 1,3, 5-Toluene (TMB) and Tetraethoxysilane (TEOS) to synthesize the mesoporous molecular sieve SBA-15, more preferably prepared by dissolving the template agent poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) in a hydrochloric acid solution, preferably stirring at 35-45 ℃, more preferably at 40 ℃ until the template agent is dissolved, adding TMB to continue stirring, preferably continuing stirring for 1-3 h, more preferably for 2h, adding TEOS to the mixed solution after stirring, preferably stirring for 5-20 min, more preferably 10min, preferably 10min after stirring, preferably for 2h, preferably for 10-30 h, preferably washing for 10-30 h, preferably for 10-30-10 h, preferably for 10-.
The method comprises the steps of performing functional amination on the surface of a mesoporous molecular sieve by using an amino-containing silane coupling agent, preferably performing reflux reaction on the amino-containing silane coupling agent and the mesoporous molecular sieve in an organic solvent under a protective atmosphere to obtain an amino-functionalized mesoporous molecular sieve, wherein the protective atmosphere is preferably nitrogen, the mass ratio of the amino-containing silane coupling agent to the mesoporous molecular sieve is preferably (0.5-4): 1, more preferably (0.5-3): 1, more preferably (0.8-1.5): 1, more preferably (0.8-1.2): 1, most preferably (1-1.2): 1, the organic solvent is preferably an alcohol solvent and more preferably absolute ethanol, the concentration of the amino-containing silane coupling agent in the reaction system is preferably 30-100 mmol/L, more preferably 40-80 mmol/L, more preferably 40-60 mmol/L, most preferably 50 mmol/L, the time of the reflux reaction is preferably 20-24 hours, after the reflux reaction is finished, the filtering is preferably performed, the drying is performed, the amino-functionalized mesoporous molecular sieve is preferably washed, and the drying is preferably performed at the temperature of the alcohol solvent is preferably 100-90 ℃, and the drying is preferably the drying is performed at the temperature is 100 ℃, and the drying is preferably 12 ℃.
Reacting the amino functionalized mesoporous molecular sieve with cyanamide; the reaction is preferably carried out in an organic solvent; the organic solvent is preferably one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and N, N-dimethylpyrrolidone (NMP); the molar ratio of primary amino groups to the cyanamide on the amino-functionalized mesoporous molecular sieve is preferably (0.5-2): 1, more preferably (0.8 to 1.5): 1; the reaction temperature is preferably 50-120 ℃, more preferably 70-100 ℃, further preferably 70-90 ℃, and most preferably 80 ℃; the reaction time is preferably 1-10 h, more preferably 3-8 h, and further preferably 4-6 h; the reaction is preferably carried out under stirring; after the reaction is finished, preferably washing the mixture to be neutral according to the sequence of absolute ethyl alcohol, water, dilute hydrochloric acid, water, an alkali solution and water, and then drying the mixture under a vacuum condition to obtain the guanidyl modified mesoporous molecular sieve; the drying temperature is preferably 60 ℃ to 80 ℃.
The preparation method of the guanidine-based modified mesoporous molecular sieve is simple, the guanidine-based modified mesoporous molecular sieve can be used for preparing thiol compounds in a catalytic manner, the conversion rate and the purity of the thiol compounds generated in the reaction process can be effectively improved, the catalyst can be recycled, the reaction period can be effectively shortened, the content of impurities in the synthesized thioether-based cyclic sulfur compounds is low, and the guanidine-based modified mesoporous molecular sieve has a good industrial application prospect.
The invention also provides a guanidino modified mesoporous molecular sieve prepared by the method, and the structure of the guanidino modified mesoporous molecular sieve is preferably as follows:
Figure BDA0002269774180000051
the invention also provides application of the guanidyl modified mesoporous molecular sieve in preparation of a mercaptan compound catalyst.
The invention also provides a preparation method of the thioether-type episulfide compound, which comprises the following steps: A1) reacting epoxy chloropropane with a first vulcanizing agent in the presence of the guanidyl modified mesoporous molecular sieve to obtain a mercaptan compound; A2) reacting the thiol compound under alkaline conditions to obtain a thioether epoxy compound; A3) and reacting the thioether epoxy compound with a second sulfur reagent to obtain the thioether epoxy sulfur compound.
Reacting epoxy chloropropane with a first vulcanizing agent in the presence of a guanidyl modified mesoporous molecular sieve to obtain a thiol compound; the molar ratio of epichlorohydrin to the first vulcanizing agent is preferably 1: (0.3 to 4), more preferably 1: (0.5-2), and more preferably 1: (0.8 to 1.5), most preferably 1: 1; the first vulcanizing agent is preferably one or more of hydrogen sulfide, sodium hydrosulfide and thiourea; the mass of the guanidyl modified mesoporous molecular sieve is preferably 0.05-10% of that of epichlorohydrin, more preferably 0.1-8%, still more preferably 0.1-5%, and most preferably 0.5-2%; the reaction temperature is preferably-20-60 ℃, more preferably 0-35 ℃, further preferably 0-15 ℃, and most preferably 2-8 ℃; the reaction time is preferably 1-4 h, more preferably, the reaction end point is the condition that no epoxy chloropropane remains in the system, and the catalyst obtained by separation can be recycled; in the invention, hydrogen sulfide is most preferably used as a vulcanizing agent, and redundant hydrogen sulfide is discharged from the system and absorbed by alkali liquor, so that the obtained product can be directly subjected to the next reaction without impurity separation.
The method comprises the steps of reacting a mercaptan compound under an alkaline condition, preferably providing an alkaline solution under the alkaline condition, preferably adding an oxidizing agent such as 1-5 mol/L, more preferably 1-4 mol/L, more preferably 2-3 mol/L, most preferably 2.5 mol/L, adding an organic base such as an inorganic base, preferably one or more of triethylamine, tributylamine, dimethylcyclohexylamine, diethylaniline and pyridine, preferably adding one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, potassium tert-butoxide, mono-hydrogen disodium phosphate and sodium acetate, preferably adding a chlorine dioxide, a chlorine, a.
Reacting the thioether epoxy compound with a second disulfide agent; the second vulcanizing agent is preferably thiourea and/or thiocyanate; the thiocyanate is preferably one or more of sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate; the molar weight of the vulcanizing agent is preferably 1-5 times, more preferably 1-3 times that of the epoxy group in the thioether epoxy compound; the reaction temperature is preferably 0-60 ℃, more preferably 10-40 ℃, further preferably 10-30 ℃, further preferably 10-20 ℃, and most preferably 10-15 ℃; the reaction time is preferably 10-30 h, more preferably 10-20 h, and further preferably 15 h; the reaction is preferably carried out under stirring; the reaction is preferably carried out in a solvent, preferably one or more of dichloromethane, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene, methanol, ethanol, isopropanol, butanol, methoxyethanol, ethylene glycol and water; after the reaction is finished, preferably washing with NaCl solution, 1% sulfuric acid solution and NaCl solution respectively, standing for layering to obtain an organic phase, dewatering with a drying agent, and filtering to remove the solvent to obtain the thioether cyclic sulfur compound. In the present invention, the thioether-based cyclic sulfur compound is preferably as follows:
Figure BDA0002269774180000071
wherein n is 0 or 1.
The invention uses guanidyl modified mesoporous molecular sieve to catalyze episulfide compound monomer required by high refractive index optical material, uses hydrogen sulfide and epichlorohydrin as raw materials, generates mercaptan compound under the catalysis of guanidyl modified mesoporous molecular sieve, and then further reacts to obtain dichlorohydrin (poly) thioether compound; after epoxidizing the epoxy resin under alkaline conditions, an epoxy group is converted into an episulfide group by using a vulcanizing agent to obtain a product. The method does not need to use a solvent in the ring-opening reaction stage of the epichlorohydrin, the separation and purification of the intermediate product are easier to carry out, the method is favorable for obtaining the high-quality episulfide compound product, the catalyst can be repeatedly used after the reaction, and the method has an industrial application prospect. In addition, in the process of preparing the thioether-like ring sulfur compound by using the synthesized guanidyl modified mesoporous molecular sieve as the catalyst, the intermediate and the final product have good quality and storage stability, the reaction process is optimized, and the purification is simple and convenient.
The polymerizable composition for optical materials containing the (di) sulfide-based episulfide compound prepared by the above-described method can be prepared by a known method, and the polymerizable composition for optical materials further contains a polyisocyanate compound and/or a polythiol compound, and the like.
The polymerizable composition containing a thioether-based episulfide compound can be used for synthesizing plastic lenses, and further can be used for various purposes such as cameras, projector lenses, prisms, optical fibers, optical filters, optical lenses for automobiles and the like, and particularly has wide application prospects in optical materials and elements such as plastic lenses, glass-plastic hybrid optical lenses used in different occasions, camera lenses and the like.
In order to further illustrate the present invention, the following will describe in detail a modified mesoporous molecular sieve with guanidino group, its preparation method and application.
The reagents used in the following examples are all commercially available.
The curing of the (di) sulfide type episulfide compound synthesized in the method of the present invention with polyisocyanate, polythiol, and the like is carried out according to the conventional method, for example, the method disclosed in patent WO2014038654A1, as briefly described below, assuming that the total amount of all the components in the polymerizable composition for optical materials is 100% by mass:
(di) thioether-type cyclic sulfur compounds: 73 parts by weight;
isophorone diisocyanate: 16 parts by weight;
bis (2-mercaptoethyl) sulfide: 10 parts by weight;
sulfur: 1 part by weight;
tetrabutylphosphonium bromide: 0.01 wt%;
dibutyl tin dichloride: 0.01 wt%;
the polymerizable composition was mixed, and then the optical material resin composition was injected into a lens mold comprising two glass plates and an adhesive tape, heated at 30 ℃ for 30 hours, then heated at a constant temperature-rising rate for 10 hours to 100 ℃, heated at 100 ℃ for 1 hour to polymerize and solidify, and after natural cooling, released from the mold, and annealed at 110 ℃ for 1 hour. The optical material after curing was tested for refractive index, Abbe number and glass transition temperature.
Example 1
Synthesis of guanidino functionalized mesoporous molecular sieve catalyst
Firstly, dissolving 4.0g P123 in 150M L concentration 1.6M HCl solution, stirring at 40 ℃ until P123 is completely dissolved, adding 0.3g of TMB into the solution, continuing stirring for 2h, adding 9.2g of TEOS into the mixed solution, stirring for 10min, standing for 24h at 40 ℃, then aging the mixture at 120 ℃ for 24h, cooling and filtering the aged mixture, washing with deionized water to neutrality, drying the washed solid at 100 ℃ under vacuum condition overnight, calcining the dried solid at 550 ℃ for 6h, wherein the temperature rise speed is 1 ℃/min, and the obtained solid is SBA-15.
In N2Under the atmosphere, 1g of the synthesized SBA-15 is added into an absolute ethyl alcohol solution 100m L of APTES with the concentration of 50mM, the mixture is filtered after refluxing for 24h, the mixture is washed by absolute ethyl alcohol and dried overnight under the vacuum condition of 80 ℃, and the obtained solid is the amino-functionalized SBA-15.
Mixing 0.5G of the prepared amino-functionalized SBA-15, a DMF solvent and 0.2G of cyanamide, heating at the temperature of 80 ℃ while stirring, reacting for 4 hours, filtering the obtained solid, washing the solid to be neutral according to the sequence of absolute ethyl alcohol, water, dilute hydrochloric acid (5 wt%), water, alkali solution (sodium sulfite, 5 wt%) and water, and drying under a vacuum condition to obtain the guanidyl modified mesoporous molecular sieve catalyst, which is marked as G/SBA-15.
The mesoporous material SBA-15 and the guanidino-modified mesoporous molecular sieve obtained in example 1 were measured for specific surface area, pore volume, and pore size distribution by adsorption using a physical adsorption apparatus. The specific surface area of the sample is calculated by adopting a multipoint Brunauer-Emmett-Teller (BET) method, the pore size distribution of the sample is calculated by adopting a Barrett-Joyner-Halenda (BJH) method, the degassing temperature of the sample is 80 ℃, the reaction temperature is-196 ℃, and the specific surface area, the pore volume and the pore size change of the SBA-15 before and after functionalization are obtained as shown in the following table 1.
TABLE 1 detection results of specific surface area, pore volume and pore diameter of mesoporous molecular sieve before and after modification
Figure BDA0002269774180000091
As can be seen from the data in the table above, the specific surface area, the pore volume and the pore diameter of SBA-15 are all reduced after guanidino functionalization, but the mesoporous structure is not damaged.
The SBA-15 and G/SBA-15 obtained in example 1 were detected by infrared spectroscopy, and the infrared spectra thereof were as shown in FIG. 1. The change of corresponding characteristic peaks can be obviously seen from the infrared absorption spectrums of SBA-15 and G/SBA-15. At a chemical shift of 2934cm-1And 2855cm-1Can see-CH respectively2The asymmetric vibration peak and the symmetric vibration peak of (1); and 3401cm-1And 1561cm-1Obvious N-H stretching vibration peak and deformation vibration peak can be observed respectively; the Si-O-Si vibrational peak and the water peak adsorbed on the sample surface were also observed at wavelengths of 1082cm-1 and 1630cm-1, respectively, and in addition, the Si-OH characteristic peak of SBA-15 at 960cm-1 disappeared after functionalization.
And (3) filtering the G/SBA-15 and then repeatedly using the filtered G/SBA-15, and calculating the activity change by dividing the amount obtained in repeated use by the amount obtained in the first time by taking the amount of the bis (2, 3-epoxypropyl) disulfide obtained in the first time as a reference to obtain a graph 2, namely an activity change trend graph of the G/SBA-15 after 20 times of repeated use. As can be seen, after 20 recycles, the G/SBA-15 still retained 87% of the initial activity.
Example 2
Synthesis of bis (2, 3-epithiopropyl) sulfide
180G of epichlorohydrin and 0.9G of the G/SBA-15 catalyst synthesized in example 1 were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser, and 70G of H was blown into the flask while stirring2S gas, the reaction temperature is kept at 2-8 ℃, the reaction time is 2 hours, no epoxy chloropropane is left in a detection system, and high-purity N is used firstly after the reaction is finished2H in the system2S is removed, and the catalyst G/SBA-15 is filtered out to obtain the chloromercaptopropanol.
Adding 200m L ethanol and 400m L toluene into chloromercaptopropanol, dropwise adding 250g of 2.5mol sodium hydroxide solution (the concentration is 40%) into the chloromercaptopropanol at the temperature of 2-8 ℃, continuing to react for 30min after the dropwise addition is finished, washing an organic layer for 3 times by using pure water after the reaction is finished, dehydrating the organic layer by using anhydrous magnesium sulfate accounting for 5% of the mass of the organic layer product, filtering, and evaporating the solvent to obtain bis (2, 3-epoxypropyl) sulfide, wherein the yield is 93.5%;
taking 100g of bis (2, 3-epoxypropyl) sulfide, adding 95g of thiourea, 200m of L ethanol and 400m of L toluene, keeping the system temperature at 10-15 ℃, stirring for reaction for 15h, washing with NaCl solution (4 wt%), 1% sulfuric acid solution and NaCl solution (4 wt%) respectively after the reaction is finished, standing for layering to obtain an organic phase, removing water with magnesium sulfate accounting for 5% of the mass of the organic phase, filtering, evaporating to remove the solvent, redissolving with acetonitrile, and evaporating to remove the solvent to obtain 79.6g of bis (2, 3-episulfide propyl) sulfide product with the content of 85.2% and the yield of 59.1%, wherein the resin obtained by curing the polymerizable composition containing the prepared bis (2, 3-episulfide propyl) sulfide has the refractive index of 1.702, the Abbe number of 36 and the vitrification temperature of 78 ℃.
Example 3
Synthesis of bis (2, 3-epithiopropyl) disulfide
180G of epichlorohydrin and 0.9G of the G/SBA-15 catalyst synthesized in example 1 were placed in a condenser tube equipped with a stirrer, a thermometerIn the four-necked flask, 70g of H was blown into the flask while stirring2S gas, the reaction temperature is kept at 2-8 ℃, the reaction time is 2 hours, no epoxy chloropropane is left in a detection system, and high-purity N is used firstly after the reaction is finished2H in the system2S is removed, and the catalyst G/SBA-15 is filtered out to obtain the chloromercaptopropanol.
Adding 200m L ethanol and 400m L toluene into chloromercaptopropanol, dropwise adding 250g of 2.5mol sodium hydroxide solution (the concentration is 40%) into the chloromercaptopropanol at the temperature of 2-8 ℃, adding 250g of iodine solid in batches in the dropwise adding process, continuing to react for 30min after dropwise adding, washing an organic layer for 3 times by using pure water after the reaction is finished, dehydrating the organic layer by using anhydrous magnesium sulfate accounting for 5% of the mass of the organic layer product, filtering, and evaporating the solvent to obtain bis (2, 3-epoxypropyl) disulfide, wherein the yield is 94%.
100g of bis (2, 3-epoxypropyl) disulfide is taken, 95g of thiourea, 200m of L ethanol and 400m of L toluene are added, the system temperature is kept at 10-15 ℃, stirring is carried out for 15h, after the reaction is finished, NaCl solution (4 wt%), 1% sulfuric acid solution and NaCl solution (4 wt%) are respectively used for washing, standing and layering are carried out to obtain an organic phase, magnesium sulfate with the mass of 5% of that of the organic phase is used for removing water, the solvent is filtered and evaporated, acetonitrile is used for redissolving, and then the solvent is evaporated to obtain 78.2g of bis (2, 3-episulfide propyl) disulfide product, the content is 84.9%, the yield is 59.0%, and the resin obtained by curing the prepared polymerizable composition containing bis (2, 3-episulfide propyl) sulfide has the refractive index of 1.738, the Abbe number of 32 and the glass transition temperature of 76 ℃.
In conclusion, the guanidyl functionalized mesoporous molecular sieve catalyst G/SBA-15 prepared by the preparation method provided by the invention has high catalytic activity, can be recycled and reused, can be used for synthesizing bis (2, 3-epoxypropyl) sulfide and bis (2, 3-epoxypropyl) disulfide by using the G/SBA-15, can obtain a product with high purity, has good product quality and less impurities, has the highest refractive index of 1.77 when being used for synthesizing resin lenses, and has wide application prospect.
Example 4
After carrying out guanidino modification on the commercial MCM-41, the modified solution is used for synthesizing bis (2, 3-epithiopropyl) sulfide:
preparation of guanidine modified MCM-41
In N2Adding 1g MCM-41 into 50mM APTES absolute ethyl alcohol solution 100m L under the atmosphere, refluxing for 24h, filtering the mixture, washing with absolute ethyl alcohol, and drying overnight under the vacuum condition of 80 ℃ to obtain a solid, namely the amino-functionalized MCM-41.
Mixing 0.5G of the prepared amino-functionalized MCM-41, a DMF solvent and 0.23G of cyanamide, heating at the temperature of 80 ℃ while stirring, reacting for 4 hours, filtering the obtained solid, washing the solid to be neutral according to the sequence of absolute ethyl alcohol, water, dilute hydrochloric acid (5 wt%), water, alkali solution (sodium sulfite, 5 wt%) and water, and drying under a vacuum condition to obtain the guanidyl modified mesoporous molecular sieve catalyst, which is marked as G/MCM-41.
G/MCM-41 is used for synthesizing bis (2, 3-epithiopropyl) sulfide
180G of epichlorohydrin and 0.95G of the synthesized G/MCM-41 catalyst were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser, and 70G of H was blown into the flask while stirring2S gas, the reaction temperature is kept at 2-8 ℃, the reaction time is 2 hours, no epoxy chloropropane is left in the system, and after the reaction is finished, high-purity N2 is used for reacting H in the system2S is removed, and the catalyst G/MCM-41 is filtered out to obtain the chloromercaptopropanol.
Adding 200m L ethanol and 400m L toluene into chloromercaptopropanol, dropwise adding 250g of 2.5mol sodium hydroxide solution (the concentration is 40%) into the chloromercaptopropanol at the temperature of 2-8 ℃, continuing to react for 30min after the dropwise addition is finished, washing an organic layer for 3 times by using pure water after the reaction is finished, dehydrating the organic layer by using anhydrous magnesium sulfate accounting for 5% of the mass of the organic layer product, filtering, and evaporating the solvent to obtain bis (2, 3-epoxypropyl) sulfide, wherein the yield is 91.7%.
Taking 100g of bis (2, 3-epoxypropyl) sulfide, adding 95g of thiourea, 200m of L ethanol and 400m of L toluene, keeping the system temperature at 10-15 ℃, stirring for reaction for 15h, washing with NaCl solution (4 wt%), 1% sulfuric acid solution and NaCl solution (4 wt%) respectively after the reaction is finished, standing for layering to obtain an organic phase, removing water with magnesium sulfate accounting for 5% of the mass of the organic phase, filtering, evaporating to remove the solvent, redissolving with acetonitrile, evaporating to remove the solvent to obtain 73.3g of bis (2, 3-episulfide propyl) sulfide product with the content of 82.7% and the yield of 57.8%, and curing the resin obtained by using the polymerizable composition containing the prepared bis (2, 3-episulfide propyl) sulfide has the refractive index of 1.701, the Abbe number of 35 and the vitrification temperature of 77 ℃.
Example 5
G/MCM-41 obtained in example 4 was used for synthesis of bis (2, 3-epithiopropyl) disulfide
180G of epichlorohydrin and 0.9G of the synthesized G/MCM-41 catalyst were placed in a four-necked flask equipped with a stirrer, a thermometer and a condenser, and 70G of H was blown into the flask while stirring2S gas, the reaction temperature is kept at 2-8 ℃, the reaction time is 2 hours, no epoxy chloropropane is left in a detection system, and high-purity N is used firstly after the reaction is finished2H in the system2S is removed, and the catalyst G/MCM-41 is filtered out to obtain the chloromercaptopropanol.
Adding 200m L ethanol and 400m L toluene into chloromercaptopropanol, dropwise adding 250g of 2.5mol sodium hydroxide solution (the concentration is 40%) into the chloromercaptopropanol at the temperature of 2-8 ℃, adding 250g of iodine solid in batches in the dropwise adding process, continuing to react for 30min after dropwise adding, washing an organic layer for 3 times by using pure water after the reaction is finished, dehydrating the organic layer by using anhydrous magnesium sulfate accounting for 5% of the mass of the organic layer product, filtering, and evaporating the solvent to obtain bis (2, 3-epoxypropyl) disulfide, wherein the yield is 92.1%.
100g of bis (2, 3-epoxypropyl) disulfide is taken, 95g of thiourea, 200m of L ethanol and 400m of L toluene are added, the system temperature is kept at 10-15 ℃, stirring is carried out for 15h, after the reaction is finished, NaCl solution (4 wt%), 1% sulfuric acid solution and NaCl solution (4 wt%) are respectively used for washing, standing and layering are carried out to obtain an organic phase, magnesium sulfate with the mass of 5% of that of the organic phase is used for removing water, the solvent is filtered and evaporated, acetonitrile is used for redissolving, and then the solvent is evaporated to obtain 76.1g of bis (2, 3-episulfide propyl) disulfide with the content of 82.3% and the yield of 54.7%, and a resin obtained by curing the prepared polymerizable composition containing bis (2, 3-episulfide propyl) sulfide has the refractive index of 1.738, the Abbe number of 31 and the vitrification temperature of 77 ℃.

Claims (3)

1. The application of the guanidyl modified mesoporous molecular sieve as a catalyst for preparing thiol compounds by using epichlorohydrin and a first vulcanizing agent is characterized in that the guanidyl modified mesoporous molecular sieve is prepared according to the following method:
s1) under a protective atmosphere, carrying out reflux reaction on an amino-containing silane coupling agent and a mesoporous molecular sieve in an organic solvent to obtain an amino-functionalized mesoporous molecular sieve; the reflux reaction time is 20-24 h;
s2) reacting the amino functionalized mesoporous molecular sieve with cyanamide to obtain a guanidyl modified mesoporous molecular sieve;
the mass ratio of the amino-containing silane coupling agent to the mesoporous molecular sieve is (0.5-4): 1;
the molar ratio of primary amino groups to cyanamide on the amino-functionalized mesoporous molecular sieve is (0.5-2): 1;
the reaction temperature in the step S2) is 50-120 ℃; the reaction time is 1-10 h.
2. Use according to claim 1, wherein the amino-containing silane coupling agent is selected from 3-aminopropyltriethoxysilane and/or 3-aminopropyltrimethoxysilane; the mesoporous molecular sieve is selected from one or more of SBA-15, MCM-41 and MCM-48.
3. A method for preparing a thioether-type episulfide compound, which is characterized by comprising the following steps:
A1) reacting epichlorohydrin with a first sulfidizing agent in the presence of the guanidinium-modified mesoporous molecular sieve of claim 1 to obtain a thiol compound;
A2) reacting the thiol compound under alkaline conditions to obtain a thioether epoxy compound;
A3) and reacting the thioether epoxy compound with a second sulfur reagent to obtain the thioether epoxy sulfur compound.
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