CN106380434B - A kind of method for preparing thiourethane co-production trithiocarbonate - Google Patents

A kind of method for preparing thiourethane co-production trithiocarbonate Download PDF

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CN106380434B
CN106380434B CN201610801951.8A CN201610801951A CN106380434B CN 106380434 B CN106380434 B CN 106380434B CN 201610801951 A CN201610801951 A CN 201610801951A CN 106380434 B CN106380434 B CN 106380434B
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thiourethane
trithiocarbonate
production
product
preparing
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CN106380434A (en
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钟宏
马鑫
王帅
曹占芳
刘广义
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms

Abstract

The invention discloses a kind of method for preparing thiourethane co-production trithiocarbonate；This method is that alkyl xanthate and halogenating agent are carried out into esterification, obtains Alkylxanthates；The Alkylxanthates carry out ammonolysis reaction with fatty amine, obtain the mixture containing thiourethane and sulfur alcohol compound；After the mixture containing thiourethane and sulfur alcohol compound carries out addition reaction under caustic alkali existence condition with carbon disulfide, separation of solid and liquid, liquid phase is thiourethane product, and solid phase is trithiocarbonic acid product salt；The product yield height of preparation technology acquisition, purity are high, and two kinds of high-efficient collecting agents of thiourethane and trithiocarbonate can be made simultaneously, and product separation is easy, Atom economy height, and production cost is low, it is easy to accomplish industrialized production.

Description

A kind of method for preparing thiourethane co-production trithiocarbonate
Technical field
It is more particularly to a kind of yellow with alkyl the present invention relates to a kind of method for preparing thiourethane co-production trithiocarbonate Ortho acid salt and benzyl halide, acrylic halogen or β-halo propionitrile are raw material, while the method for producing thiourethane and trithiocarbonate, Belong to the preparation field of flotation collector.
Background technology
Thiourethane, scientific name are O- alkyl-N- alkylthio carbamates, are a kind of sulfide flotation medicines of function admirable Agent, it has excellent chelation to metal ions such as copper, gold, silver, sulfide mineral collector such as xanthate, black powder etc. with routine Compared to selectivity it is good, dosage is small, have foaming characteristic, valuable mineral can be realized under the conditions of low alkali and gangue mineral it is effective The advantages that separation, thus be widely used in the flotation of various copper mines, gold mine, Pb-Zn deposits, be apply and study in modern age flotation it is more A kind of nonionic sulfide mineral collector.Different, the preparation method master of thiourethane class collecting agent according to the basic material used It is divided into two classes, one kind is the raw material based on xanthate, another kind of, is the raw material based on rhodanate.Based on xanthate The method of Material synthesis has：Alkyl halide esterification process (United States Patent (USP) US2691635), chloroacetic acid esterification method (United States Patent (USP) US3224864；Yang Haiyan, improvement [J] the Shaanxi chemical industry of Li Musong thiourethane floating agent production technologies, 1999,28 (1): 42-43.), a step catalysis synthesis process (United States Patent (USP) US5041599) and dimethyl sulfate ester process (Chinese patent CN1169988)；With There is the synthetic method of raw material based on rhodanate：Phase transfer catalysis process (United States Patent (USP) US4482500) and organic solvent method (in State patent CN1153774A).Alkyl halide esterification process is using xanthates as raw material, after alkyl halide (such as monochloro methane) esterification, with Low-grade alkylamine effect generation thiourethane, this method require higher to equipment and esterification temperature, and product is not easily purified, and can be produced Raw largely industrial wastewater and waste gas containing methyl mercaptan, it is big for environment pollution.One step catalysis synthesis process is that xanthate exists with alkylamine Thiourethane is directly synthesized in the presence of catalyst, this method technique is simple, but product yield is low, expensive catalyst and is difficult to back Receive, cause production cost high, there are a large amount of waste water sulfides to produce, pollute environment.Dimethyl sulfate ester process is with isopropyl xanthan acid Sodium is raw material, reacts to obtain O- isopropyls-S- methyl-dithiocarbonates intermediate with dimethyl suflfate, then again with ethamine Carry out aminolysis reaction and thiourethane is made, the technique is simpler, and product quality is also higher, but its used dimethyl suflfate Matter is unstable, is easily hydrolyzed into sulfuric acid and methanol, it is difficult to realizes the large-scale production of industry, and accessory substance methyl mercaptan is difficult to inhale Receive and utilize, cause environmental pollution.Phase transfer catalysis process is the rhodanate aqueous solution and organic halogen in phase transfer catalyst In the presence of react be made thiourethane, the complex process, reactions steps are more, and process is discontinuous, a small amount of organic intermediate with mutually turn Shifting catalyst causes certain pollution to environment with the loss of aqueous phase.Organic solvent method is that rhodanate exists with organic halogen Higher alcohols dicyandiamide solution reaction generation thiourethane, the complex process, product yield is low, therefore also fails to be used widely.Mesh Preceding industrial production thiourethane mainly uses chloroacetic acid esterification method, and this method is that the chloro in alkyl chloride esterification process is replaced with monoxone Alkane, monoxone and sodium carbonate are esterified after reacting generation sodium chloroacetate with xanthate, then generate sulphur ammonia with low-grade alkylamine effect Ester.The process conditions are gentle, and yield is high, good product quality, but cost is higher, thus expensive, limits thiourethane collecting Extensive use of the agent in flotation.And because byproduct TGA impurity is more, purification difficulty is big, can only be used as copper-cobalt ore Inhibitor, the market demand is few, limits the large-scale application of the technique.
Trithiocarbonate is a kind of sulfydryl collecting agent, and the O that it can be regarded as in S atom substitution xanthates molecule is former The derivative of son.It has good collecting effect to galena, molybdenite, auriferous pyrite etc., especially in recovery platinum family gold During category, the rate of recovery of platinum and the grade of concentrate platinum group metal can be improved, efficiently solves traditional collecting agent to platinum family The problems such as the floatability of metalliferous mineral is low.Because the cost of material of existing technology of preparing is higher, extensive use is not yet obtained.
The content of the invention
The defects of existing for the existing method for preparing thiourethane and trithiocarbonate, it is an object of the invention to carry For a kind of achievable thiourethane and trithiocarbonate Joint Production, and high yield obtains high-purity thiourethane and trithiocarbonic acid The method of salt, this method have the characteristics that simple to operate, raw material availability is high, cost is low, environmentally friendly, it is easy to accomplish industry Metaplasia is produced.
In order to realize above-mentioned technical purpose, the invention provides a kind of side for preparing thiourethane co-production trithiocarbonate Method, this method comprise the following steps：
1) alkyl xanthate and halogenating agent carry out esterification, obtain Alkylxanthates；The halogenating agent is Benzyl halide, acrylic halogen or β-halo propionitrile；
2) Alkylxanthates and fatty amine carry out ammonolysis reaction, obtain mixed containing thiourethane and sulfur alcohol compound Compound；Described sulfur alcohol compound is benzyl mercaptan, propene thiol or propionitrile base mercaptan；
3) mixture containing thiourethane and sulfur alcohol compound is carried out under caustic alkali existence condition with carbon disulfide After addition reaction, separation of solid and liquid, liquid phase is thiourethane product, and solid phase is trithiocarbonic acid product salt.
Technical scheme key is to replace conventional chloro using the halogenating agent containing benzyl, alkenyl or cyano group Alkane carries out esterification with alkyl xanthate and changes into Alkylxanthates intermediate product, then is tried halo by ammonolysis reaction Agent changes into mercaptan compound, and alkyl xanthate changes into thiourethane indirectly, and sulfur alcohol compound is direct without separation Reaction generation trithiocarbonate is carried out with carbon disulfide and caustic alkali, then by two-phase laminated flow, obtain high-purity three are thio Carbonate and thiourethane product.Traditional halogenated alkane is replaced using the halogenating agent of the present invention to be produced, and is existed obvious Advantage：1) benzyl halide, acrylic halogen and β-halo propionitrile substitute halogen due to conjugatedπbond or the subbase group of short of electricity containing polarity The reactivity of base is big, it is easy to substitution reaction occurs, greatly reduces the temperature conditionss of esterification, improves yield；2) pass After the halogenated alkane of system changes into small molecule mercaptan, water can be dissolved in and produce organic wastewater, and volatile, foul smelling, to environment Influence halogenating agent that is big, and using the present invention, the sulfur alcohol compound of generation without separation, can further with carbon disulfide Reaction obtains the trithiocarbonic acid product salt that can also serve as collecting agent, and avoids the generation of waste water and gas；3) using this For the halogenating agent of invention as raw material, the trithiocarbonate being eventually converted into is solid product, and insoluble in thiourethane, is held Easy Precipitation, when solving existing halogenated alkane as raw material, thiourethane be difficult to separation the problem of.
Preferable scheme, the alkyl xanthate of formula 1 and the halogenating agent of formula 2 carry out esterification, obtain the alkyl xanthogenic acid of formula 3 Ester；
R2-X
Formula 2
Wherein, R1For C1~C8Alkyl；R2For benzyl, acrylic or propionitrile base；M is alkali metal；X is halogen.
More preferably scheme, the condition of the esterification are：Reaction temperature be 50~100 DEG C, the reaction time be 1~ 8h。
More preferably scheme, the mol ratio of the halogenating agent and alkyl xanthate is 0.9~1.1:1.0.
Preferable scheme, M K, Na etc., X Cl, Br, I etc..
More preferably scheme, the esterification use with 3) in thiourethane product identical thiourethane as solvent.It is logical Cross and use with target thiourethane product identical thiourethane as solvent, on the one hand, intermediate product Alkylxanthates, thio-alcohol Compound etc. can be dissolved in the solvent, can improve reaction efficiency, and trithiocarbonate is solid, and be substantially insoluble in sulphur ammonia Ester, it is only necessary to which simple filter operation can effectively realize the separation of trithiocarbonate；Another aspect thiourethane solvent and reaction The thiourethane product of generation is identical, without separating-purifying, can greatly simplify technique, no industrial wastewater produces, it is easy to accomplish work Industry metaplasia is produced.
Further preferred scheme, the thiourethane dosage as solvent are 1~8 times of alkyl xanthogenic acid salt quality.
Preferable scheme, after the Alkylxanthates carry out ammonolysis reaction with the fatty amine of formula 4, it is inorganic to be separated by filtration removal Salt, obtain the mixture containing the thiourethane of formula 5 and sulfur alcohol compound；
R3-NH2
Formula 4
Wherein, R1And R3Independently selected from C1~C8Alkyl.
More preferably scheme, the condition of the ammonolysis reaction are：Reaction temperature be 30~100 DEG C, the reaction time be 1~ 5h；
More preferably scheme, the addition of the fatty amine are 0.9~1.1 times of alkyl xanthate mole.
Preferable scheme, 3) addition of carbon disulfide is 0.9~1.2 times of alkyl xanthate mole in；
Preferable scheme, 3) addition of caustic alkali is 0.9~1.2 times of alkyl xanthate mole in.
Preferable scheme, 3) reaction temperature in is 5~80 DEG C, and the reaction time is 2~8h.
More preferably scheme, caustic alkali include sodium hydroxide and/or potassium hydroxide.
The trithiocarbonate prepared in technical scheme has the structure of formula 6：
Wherein, R2For benzyl, acrylic or propionitrile base；M is alkali metal.
It is inorganic in reaction solution after Alkylxanthates carry out ammonolysis reaction with fatty amine in technical scheme Salt is directly isolated by filtration, and prevents it from entering in follow-up trithiocarbonic acid product salt.
More preferably scheme, alkyl xanthate are alkyl xanthogenic acid sodium or alkyl xanthogenic acid potassium.
More preferably scheme, halogen is chlorine, bromine or iodine in halogenating agent.
More preferably scheme, fatty amine include methylamine, ethamine, propylamine or butylamine.
The present invention synthetic reaction principle be：In organic solvent system, alkyl xanthate and benzyl halide, acrylic halogen, Substitution reaction occurs for the electrophilic reagents such as β-halo propionitrile, generates xanthic acid ester type compound, reaction equation such as reaction equation (1) institute Show：
Reaction equation (1)：
Nucleophilic substitution occurs for the nucleopilic reagent such as xanthic acid ester type compound and low-grade aliphatic amine, obtains target product sulphur Urethane and sulfur alcohol compound, shown in reaction equation such as reaction equation (2)：
Reaction equation (2)：
React sulfur alcohol compound and carbon disulfide, caustic alkali reaction generation trithiocarbonate and water, the reaction of gained Shown in equation such as reaction equation (3)：
Reaction equation (3)：
Compared with the prior art, the beneficial effect that technical scheme is brought：
(1) technical scheme is most with alkyl xanthate and benzyl halide, acrylic halogen or β-halo propionitrile etc. First raw material obtains two kinds of chemical products of thiourethane and trithiocarbonate simultaneously, and Atom economy is high, and product yield is high, pure Degree is high, significantly reduces the production cost of thiourethane collecting agent and trithiocarbonate.
(2) intermediate product and final product in technical scheme per single step reaction all can be easily separated, it is only necessary to It can be achieved by settling and being separated by filtration, enormously simplify processing step, product loss late is low, can reduce production cost, have Beneficial to industrialized production.
(3) technical scheme has prevented industrial waste gas substantially and waste water produces, and reduces three-protection design cost, has Beneficial to environmental protection.
Brief description of the drawings
【Fig. 1】For the ultraviolet spectrogram of O- isopropyl-N- ethyl thiocarbamates；
【Fig. 2】For the infrared spectrogram of O- isopropyl-N- ethyl thiocarbamates；
【Fig. 3】For the total ion current figure of O- isopropyl-N- ethyl thiocarbamates；
【Fig. 4】For the mass spectrogram of O- isopropyl-N- ethyl thiocarbamates；
【Fig. 5】For the infrared spectrogram of O- isobutyl group-N- ethyl thiocarbamates；
【Fig. 6】For the infrared spectrogram of benzyl trithiocarbonic acid sodium；
【Fig. 7】For the ultraviolet spectrogram of isopropyl xanthan acid benzyl ester；
【Fig. 8】For the infrared spectrogram of isopropyl xanthan acid benzyl ester；
【Fig. 9】For the mass spectrogram of isopropyl xanthan acid benzyl ester.
Embodiment
The present invention is further illustrated by following examples, but is not restricted by the embodiments.All numbers in embodiment Quality is unless otherwise specified referred both to percentage.
Embodiment 1
Synthesize O- isopropyl-N- ethyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
It is by O- isopropyl-N- ethyl thiocarbamates that 30.32 parts of purity are 95.12% and 17.53 parts of purity 90.27% sodium isopropyl xanthate is added in reactor, is sufficiently stirred, then pure with 12.79 parts of constant pressure funnel addition It is 75 DEG C to spend for 99.0% benzyl chloride, controlling reaction temperature, and reaction is cooled to room temperature after 3 hours, then uses constant pressure funnel 6.68 parts of ethylamine solutions (content is 65%~70%) are added, 70 DEG C is warming up to, reacts 2 hours, room temperature is cooled to and crosses and filter out Sodium chloride is removed, filtrate be transferred to reactor, 8.08 parts of purity are added into reactor and are 99.0% carbon disulfide, and are added 4.38 parts of powdered sodium hydroxides (purity 96.0%), after adding sodium hydroxide, in 30 DEG C of stirring reactions 4 hours, reaction knot Beam.It is filtrated to get benzyl trithiocarbonic acid sodium collecting agent and O- isopropyl-N- ethyl thiocarbamate collecting agents.Analytical table Bright O- isopropyls-N- ethyl thiocarbamates product purity is 92.08%, the product yield based on sodium isopropyl xanthate For 94.23%；Benzyl trithiocarbonic acid sodium purity is 82.75%, and the product yield based on sodium isopropyl xanthate is 94.89%.O- isopropyls-N- ethyl thiocarbamates product is carried out after saturated common salt water washing, separated purification Characterize, ultraviolet spectra, infrared spectrum, total ion current figure, the mass spectrogram of product are shown in Fig. 1~Fig. 4 respectively, and its infrared spectrum feature is inhaled Receiving peak has (KBr, cm-1)：3264.38(νNH), 2978.34,2875.10 (νCH3), 2934.85 (νCH2), 1521.42 (νCN), 1213.11(νCOC), 1054.25 (νC=S).Benzyl trithiocarbonic acid sodium product is characterized after recrystallization, and its infrared spectrum is shown in Fig. 6, characteristic absorption peak have (KBr, cm-1)：1017.39(νC=S), 911.90 (νC-S), 1595.10,1580.48,733.22, 700.11(νPhenyl ring), 1611.42,1493.16,1451.85 (νPhenyl ring C=C)。
Embodiment 2
Synthesize O- isobutyl group-N- ethyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
It is by O- isobutyl group-N- ethyl thiocarbamates that 25.30 parts of purity are 94.77% and 18.84 parts of purity 91.41% sodium isobutyl xanthan is added in reactor, is sufficiently stirred, then pure with 12.79 parts of constant pressure funnel addition It is 65 DEG C to spend for 99.0% benzyl chloride, controlling reaction temperature, reacts 2 hours, is cooled to room temperature, is then added with constant pressure funnel Enter 6.68 parts of ethylamine solutions (content is 65%~70%), be warming up to 70 DEG C, react 2 hours, be cooled to room temperature and be filtered to remove Sodium chloride, reactor is filtrate be transferred to, 8.08 parts of purity are added into reactor and are 99.0% carbon disulfide, and are added 4.38 parts of powdered sodium hydroxides (purity 96%), after adding caustic alkali, in 30 DEG C of stirring reactions 4 hours, reaction terminated.Cross Filter obtains benzyl trithiocarbonic acid sodium collecting agent and O- isobutyl group-N- ethyl thiocarbamate collecting agents.Analysis shows O- Isobutyl group-N- ethyl thiocarbamates product purity is 91.94%, and the product yield based on sodium isobutyl xanthan is 94.88%；Benzyl trithiocarbonic acid sodium purity is 83.29%, and the product yield based on sodium isobutyl xanthan is 95.07%. O- isobutyl groups-N- ethyl thiocarbamates product is characterized after saturated common salt water washing, separated purification, product Infrared spectrum is shown in Fig. 5, and its characteristic absorption peak has (KBr, cm-1)：3266.67(νNH), 2965.14,2875.41 (νCH3), 1523.65(νCN), 1205.10 (νCOC), 1055.87 (νC=S).Benzyl trithiocarbonic acid sodium product carries out table after recrystallization Sign, its infrared spectrum are shown in Fig. 6, and its characteristic absorption peak has (KBr, cm-1)：1017.39(νC=S), 911.90 (νC- S), 1595.10、1580.48、733.22、700.11(νPhenyl ring), 1611.42,1493.16,1451.85 (νPhenyl ring C=C)。
Embodiment 3
Synthesize O- isopropyl-N- propyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
It is by O- isopropyl-N- propyl thiocarbamates that 114.95 parts of purity are 95.12% and 53.59 parts of purity 90.27% sodium isopropyl xanthate is added in reactor, is sufficiently stirred, then pure with 38.37 parts of constant pressure funnel addition It is 75 DEG C to spend for 99.0% benzyl chloride, controlling reaction temperature, reacts 3 hours, is cooled to room temperature, is then added with constant pressure funnel Enter the n-propylamine that 18.09 parts of purity are 98.0%, be warming up to 70 DEG C, react 3 hours, be cooled to room temperature filtration from sodium chloride, Reactor is filtrate be transferred to, the carbon disulfide that 25.38 parts of purity are 99.0% is added into reactor, and add 13.13 parts Powdered sodium hydroxide (purity 96%), after adding caustic alkali, in 30 DEG C of stirring reactions 4 hours, reaction terminated.It is filtrated to get Benzyl trithiocarbonic acid sodium collecting agent and O- isopropyl-N- propyl thiocarbamate collecting agents.Analysis shows O- isopropyls- N- propyl thiocarbamates product purity is 90.62%, and the product yield based on sodium isopropyl xanthate is 90.17%； Benzyl trithiocarbonic acid sodium purity is 80.15%, and the product yield based on sodium isopropyl xanthate is 89.93%.
Embodiment 4
Synthesize O- isobutyl group-N- propyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
It is by O- isobutyl group-N- propyl thiocarbamates that 94.89 parts of purity are 95.12% and 28.26 parts of purity 91.41% sodium isobutyl xanthan is added in reactor, is sufficiently stirred, then pure with 19.19 parts of constant pressure funnel addition It is 75 DEG C to spend for 99.0% benzyl chloride, controlling reaction temperature, reacts 3 hours, is cooled to room temperature, is then added with constant pressure funnel Enter the n-propylamine that 9.05 parts of purity are 98.0%, be warming up to 70 DEG C, react 3 hours, cooled and filtered removes sodium chloride, by filtrate Reactor is transferred to, the carbon disulfide that 12.69 parts of purity are 99.0% is added into reactor, and add 6.56 parts of powdered hydrogen Sodium oxide molybdena (purity 96%), after adding caustic alkali, in 30 DEG C of stirring reactions 4 hours, reaction terminated.It is filtrated to get benzyl trithio For sodium carbonate collecting agent and O- isobutyl group-N- propyl thiocarbamate collecting agents.Analysis shows O- isobutyl group-N- propylthios It is 90.77% for urethane product purity, the product yield based on sodium isobutyl xanthan is 90.85%；Benzyl trithio It is 81.24% for sodium carbonate purity, the product yield based on sodium isobutyl xanthan is 91.07%.
Embodiment 5
Synthesize O- ethyl-N- ethyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
O- isopropyl-N- the ethyl thiocarbamates that 30.32 parts of purity are 95.12% in embodiment 1 are substituted for O- ethyl-N- the ethyl thiocarbamates that 28.65 parts of purity are 93.76%, the isopropyl that 17.53 parts of purity are 90.27% Base sodium xanthogenate is substituted for the sodium ethylxanthate that 15.86 parts of purity are 90.92%, the other the same as in Example 1.Analysis shows O- second Base-N- ethyl thiocarbamates product purity is 93.14%, and the product yield based on sodium ethylxanthate is 94.56%； Benzyl trithiocarbonic acid sodium purity is 84.67%, and the product yield based on sodium ethylxanthate is 95.16%.The O- that will be obtained Ethyl-N- ethyl thiocarbamate products make solvent, by above-mentioned steps in triplicate, O- ethyl-N- ethylenebis dithiocarbamate amino Formic acid esters product purity is more than 93%, and the product yield based on sodium ethylxanthate is more than 94%；Benzyl trithiocarbonic acid Sodium purity is more than 84%, and the product yield based on sodium ethylxanthate is more than 94%.
Embodiment 6
Synthesize O- butyl-N- ethyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
O- isopropyl-N- the ethyl thiocarbamates that 30.32 parts of purity are 95.12% in embodiment 1 are substituted for O- butyl-N- the ethyl thiocarbamates that 32.50 parts of purity are 94.18%, the isopropyl that 17.53 parts of purity are 90.27% Base sodium xanthogenate is substituted for the sodium n-butyl-xanthate that 18.67 parts of purity are 92.25%, the other the same as in Example 1.Analysis shows O- fourths Base-N- ethyl thiocarbamates product purity is 94.27%, and the product yield based on sodium n-butyl-xanthate is 94.88%； Benzyl trithiocarbonic acid sodium purity is 83.06%, and the product yield based on sodium n-butyl-xanthate is 94.76%.The O- that will be obtained Butyl-N- ethyl thiocarbamate products make solvent, by above-mentioned steps in triplicate, O- butyl-N- ethylenebis dithiocarbamate amino Formic acid esters product purity is more than 94%, and the product yield based on sodium n-butyl-xanthate is more than 94%；Benzyl trithiocarbonic acid Sodium purity is more than 83%, and the product yield based on sodium n-butyl-xanthate is more than 94%.
Embodiment 7
Synthesize O- isopropyl-N- butyl thiocarbamate coproduction benzyl trithiocarbonic acid sodium：
O- isopropyl-N- the ethyl thiocarbamates that 30.32 parts of purity are 95.12% in embodiment 1 are substituted for 35.00 parts of purity are 91.93% O- isopropyl-N- butyl thiocarbamates, and (content is for 6.68 parts of ethylamine solutions 65%~70%) 7.50 parts of butylamine (purity 98%), the other the same as in Example 1 are substituted for.Analysis shows O- isopropyl-N- butyl Thiocarbamate product purity is 92.31%, and the product yield based on sodium isopropyl xanthate is 93.51%；Benzyl three Sodium thiocarbonate purity is 82.19%, and the product yield based on sodium isopropyl xanthate is 95.07%.The O- isopropyls that will be obtained Base-N- butyl thiocarbamate products make solvent, by above-mentioned steps in triplicate, O- isopropyl-N- butyl sulfo-aminos Formic acid esters product purity is more than 92%, and the product yield based on sodium isopropyl xanthate is more than 93%；Three thio carbon of benzyl Sour sodium purity is more than 82%, and the product yield based on sodium isopropyl xanthate is more than 95%.
Embodiment 8
O- isopropyl-N- ethyl thiocarbamate coproduction diallyl trisulfides are synthesized for potassium carbonate：
It is that to be substituted for 7.73 parts of purity be 99.0% chloropropene to 99.0% benzyl chloride by 12.79 parts of purity in embodiment 1, 4.38 parts of powdered sodium hydroxides (purity 96.0%) are substituted for 6.55 parts of powdered potassium hydroxides (purity 90.0%), its It is the same as embodiment 1.Analysis shows O- isopropyl-N- ethyl thiocarbamates product purity is 91.11%, based on isopropyl The product yield of sodium xanthogenate is 92.73%；Diallyl trisulfide is 80.23% for potassium carbonate purity, based on isopropyl xanthan acid The product yield of sodium is 93.76%.Obtained O- isopropyl-N- ethyl thiocarbamate products are made into solvent, by above-mentioned In triplicate, O- isopropyl-N- ethyl thiocarbamates product purity is more than 91% to step, based on isopropyl xanthan acid The product yield of sodium is more than 92%；Diallyl trisulfide is more than 80% for potassium carbonate purity, based on sodium isopropyl xanthate Product yield is more than 93%.

Claims (10)

  1. A kind of 1. method for preparing thiourethane co-production trithiocarbonate, it is characterised in that：Comprise the following steps：
    1) alkyl xanthate and halogenating agent carry out esterification, obtain Alkylxanthates；The halogenating agent is benzyl Halogen, acrylic halogen or β-halo propionitrile；
    2) Alkylxanthates carry out ammonolysis reaction with fatty amine, obtain the mixing containing thiourethane and sulfur alcohol compound Thing；Described sulfur alcohol compound is benzyl mercaptan, propene thiol or propionitrile base mercaptan；
    3) mixture containing thiourethane and sulfur alcohol compound carries out addition under caustic alkali existence condition with carbon disulfide After reaction, separation of solid and liquid, liquid phase is thiourethane product, and solid phase is trithiocarbonic acid product salt.
  2. 2. the method according to claim 1 for preparing thiourethane co-production trithiocarbonate, it is characterised in that：The alkane of formula 1 Base xanthates and the halogenating agent of formula 2 carry out esterification, obtain the Alkylxanthates of formula 3；
    R2X
    Formula 2
    Wherein, R1For C1~C8Alkyl；R2For benzyl, acrylic or β-propionitrile base；M is alkali metal；X is halogen.
  3. 3. the method according to claim 2 for preparing thiourethane co-production trithiocarbonate, it is characterised in that：
    The condition of the esterification is：Reaction temperature is 50~100 DEG C, and the reaction time is 1~8h；
    The mol ratio of the halogenating agent and alkyl xanthate is 0.9~1.1:1.0.
  4. 4. the method for preparing thiourethane co-production trithiocarbonate according to any one of claims 1 to 3, its feature exist In：The esterification use with 3) in thiourethane product identical thiourethane as solvent.
  5. 5. the method according to claim 4 for preparing thiourethane co-production trithiocarbonate, it is characterised in that：As molten The thiourethane dosage of agent is 1~8 times of alkyl xanthogenic acid salt quality.
  6. 6. the method according to claim 1 or 2 for preparing thiourethane co-production trithiocarbonate, it is characterised in that：Institute State after Alkylxanthates and the fatty amine of formula 4 carry out ammonolysis reaction, be separated by filtration removal inorganic salts, obtain containing the thiourethane of formula 5 and The mixture of sulfur alcohol compound；
    Wherein, R1And R3Independently selected from C1~C8Alkyl.
  7. 7. the method according to claim 6 for preparing thiourethane co-production trithiocarbonate, it is characterised in that：
    The condition of the ammonolysis reaction is：Reaction temperature is 30~100 DEG C, and the reaction time is 1~5h；
    The addition of the fatty amine is 0.9~1.1 times of alkyl xanthate mole.
  8. 8. the method according to claim 1 for preparing thiourethane co-production trithiocarbonate, it is characterised in that：
    3) addition of carbon disulfide is 0.9~1.2 times of alkyl xanthate mole in；
    3) addition of caustic alkali is 0.9~1.2 times of alkyl xanthate mole in.
  9. 9. the method for preparing thiourethane co-production trithiocarbonate according to claim 1 or 8, it is characterised in that：3) In reaction temperature be 5~80 DEG C, the reaction time is 2~8h.
  10. 10. the method for preparing thiourethane co-production trithiocarbonate according to claim 1 or 8, it is characterised in that：Institute The caustic alkali stated includes sodium hydroxide and/or potassium hydroxide.
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