CN110724077A - Preparation method of 1,2, 3-trithio-ethyl-thiopropane - Google Patents
Preparation method of 1,2, 3-trithio-ethyl-thiopropane Download PDFInfo
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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Abstract
The invention discloses a preparation method of 1,2, 3-trithio-ethyl-thiopropane, which comprises the steps of firstly reacting trichloropropane with mercaptoethanol to obtain an intermediate triol compound, and then reacting the triol compound with waste gas H2And S, carrying out catalytic reaction to finally obtain the 1,2, 3-trithio-ethyl-thiopropane. The preparation method greatly improves the atom utilization rate in the synthesis process, belongs to waste gas recycling, reduces the raw material cost, is economical and environment-friendly, and is particularly suitable for the existing environment-friendly large situation.
Description
Technical Field
The invention belongs to the field of chemical technology, and particularly relates to a preparation method of 1,2, 3-trithioethyl thiopropane.
Background
Sulfur-containing vinyl resins have received much attention because of their relatively high refractive index and low dispersion properties. The resin-polythiourethane formed by polymerizing polythiol and isocyanate has better performance. The existing document molecular design of polymer optical resin and novel optical plastics discloses a method for synthesizing 1,2, 3-trimercapto ethyl thiopropane, which comprises the steps of firstly reacting trichloropropane with mercaptoethanol to obtain an intermediate triol compound, then carrying out sulfhydrylation reaction on the intermediate triol compound, thiourea and hydrochloric acid, adding ammonia water for alkaline hydrolysis after the reaction is finished, adjusting acid, washing with ethanol, and removing small molecules to obtain the 1,2, 3-trimercapto ethyl thiopropane. The method has more process flows, the sulfhydrylation needs to be carried out by thiourea and hydrochloric acid, a large amount of ammonia water needs to be added for alkaline hydrolysis, a large amount of acid needs to be added for neutralization of alkaline hydrolysis waste liquid, the operation is complex, the atom economy is not high, and a large amount of acid waste water is caused because a large amount of inorganic acid and alkali are needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of 1,2, 3-trithio-ethyl-thiopropane, which comprises the steps of firstly reacting trichloropropane with mercaptoethanol to obtain an intermediate triol compound, and then reacting the intermediate triol compound with waste gas H2And S is reacted to finally obtain the 1,2, 3-trithio-ethyl-thiopropane. The preparation method greatly improves the atom utilization rate in the synthesis process, belongs to waste gas recycling, reduces the raw material cost, is economical and environment-friendly, and is particularly suitable for the existing environment-friendly large situation.
The technical scheme of the invention is realized as follows:
a process for preparing 1,2, 3-trithio ethyl thiopropane includes reaction of trichloropropane with mercaptoethanol to obtain intermediate triol compound A, and reaction between triol compound A and waste gas H2And S, carrying out catalytic reaction to finally obtain the 1,2, 3-trithio-ethyl-thiopropane. The reaction equation is as follows:
the method comprises the following specific steps:
(1) adding trichloropropane and mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to cool, heating in a water bath to 85-90 ℃, slowly dropwise adding 50% KOH solution in percentage by mass, wherein mauve appears in the dropwise adding process, the solution gradually becomes colorless when the KOH is nearly dripped, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to neutrality;
(2) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules;
(3) putting the obtained triol compound A into a high-pressure reaction kettle, adding a catalyst, and then introducing H2And S, reacting, filtering out the catalyst after the reaction is finished, washing the filtrate with acid, washing the filtrate with ethanol, and removing small molecules to obtain colorless or slightly yellow liquid, namely the 1,2, 3-trithioethyl thiopropane.
The molar ratio of the mercaptoethanol to the trichloropropane in the step (1) is 2.98-3.3, and the molar ratio of the KOH to the trichloropropane is 1.0-1.05.
H in the step (3)2The amount of S to be added is 3 to 5 times, preferably 3.2 to 3.7 times, the molar equivalent of the triol compound A. Wherein H2S is introduced in a gas form, and the flow rate is 0.5L-1.2L/h. The reaction conditions in the step (3): the reaction temperature is 200 ℃ and 500 ℃, the reaction pressure is 0.2-1.5MP, and the reaction time is 4-9 h; preferably, the reaction conditions are: the reaction temperature is 200 ℃ and 300 ℃, the reaction pressure is 0.5-0.9MPa, and the reaction time is 6-8 h.
The catalyst is a molecular sieve catalyst, and the catalyst is preferably gamma-Al2O3Silica gel; the catalyst is preferably supported Ni-Mo, Ni-W, Co-Mn, Co-W, KOH, K2WO4、CsWO4gamma-Al of (2)2O3(ii) a The catalystThe agent is preferably supported K2WO4、CsWO4gamma-Al of (2)2O3(ii) a The gamma-Al2O3Upper load K2WO4、CsWO4The loading amount of (B) is 1% wt to 12% wt, preferably 2% wt to 5% wt. The load amount here refers to a mass ratio.
The catalyst is a molecular sieve catalyst which is high in selectivity and activity, uniform and regular microporous structures are distributed in the molecular sieve, and molecules of the manholes are limited by different pore sizes, so that the catalyst has high selectivity.
The sulfhydrylation process of the invention is to directly react the intermediate triol compound with the waste gas H2S reaction, then acid washing and ethanol washing are carried out, and the product 1,2, 3-trithio-ethyl-thiopropane is directly obtained, so that the method is more economical and environment-friendly, namely: by means of exhaust gases H2S is used as a sulfur source to replace the traditional thiourea and hydrochloric acid scheme, so that the synthesis cost can be effectively reduced, the yield is improved, and the green and environment-friendly concept is met; the synthetic route is simple and feasible, and is suitable for industrial large-scale production.
Example 1
(1) Sequentially adding 0.5mol of trichloropropane and 1.5mol of mercaptoethanol into a four-neck flask, introducing nitrogen to reduce the temperature, heating in a water bath to 85-90 ℃, slowly dropwise adding 0.5mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, when the KOH is nearly dripped, the solution gradually becomes colorless, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to neutrality;
(2) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules;
(3) putting the obtained triol compound A into a high-pressure reaction kettle, and adding 5% wtCsWO4/γ-Al2O3The catalyst is then introduced into the reactor at a flow rate of 1L/H2S，H2The adding amount of S is 3.5 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 250 ℃, and the reaction pressure is 0.9 MPa; the reaction time is 8 h. Filtering out the catalyst after the reaction is finished, pickling the filtrate, washing the filtrate with ethanol, and removing the catalystGetting out small molecules to obtain colorless or slightly yellow liquid, namely the product 1,2, 3-trithiol ethyl thiopropane with the yield of 88 percent and nd(refractive index) 1.6409.
Example 2
(1) Adding 0.5mol of trichloropropane and 1.49mol of mercaptoethanol into a four-neck flask in sequence, introducing nitrogen for cooling, heating in a water bath to 85-90 ℃, slowly dropwise adding 0.525mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, when the KOH is nearly dripped, the solution gradually becomes colorless, then quickly adding the rest KOH, and then adding concentrated HCl for acidification to neutrality.
(2) And (3) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules.
(3) Putting the obtained triol compound A into a high-pressure reaction kettle, and adding 5 wt% of K2WO4/γ-Al2O3The catalyst was then introduced into the reactor at a flow rate of 0.5L/H2S，H2The adding amount of S is 3.7 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 200 ℃, and the reaction pressure is 0.5 MPa; the reaction time is 6 h. After the reaction is finished, the catalyst is filtered, the filtrate is washed by acid and then washed by ethanol to remove small molecules, and colorless or slightly yellow liquid, namely the product 1,2, 3-trithioethyl thiopropane, is obtained, the yield is 87 percent, and n isd＝1.6407。
Example 3
(1) Adding 0.5mol of trichloropropane and 1.65mol of mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to reduce the temperature, heating the flask to 85-90 ℃ in a water bath, slowly dropwise adding 0.505mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, gradually changing the solution into colorless when the KOH is nearly dripped, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to be neutral.
(2) And (3) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules.
(3) Putting the obtained triol compound A into a high-pressure reaction kettle, and adding 3％wtNi-Mo/γ-Al2O3The catalyst is then introduced into the reactor at a flow rate of 0.6L/H2S，H2The adding amount of S is 3.2 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 300 ℃, and the reaction pressure is 0.2 MPa; the reaction time was 9 h. After the reaction is finished, the catalyst is filtered, the filtrate is washed by acid and then washed by ethanol to remove small molecules, and colorless or slightly yellow liquid, namely the product 1,2, 3-trithioethyl thiopropane, is obtained, the yield is 85 percent, and n isd＝1.6405。
Example 4
(1) Adding 0.5mol of trichloropropane and 1.6mol of mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to reduce the temperature, heating the flask to 85-90 ℃ in a water bath, slowly dropwise adding 0.51mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, when the KOH is nearly dripped, the solution gradually becomes colorless, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to be neutral.
(2) And (3) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules.
(3) Putting the obtained triol compound A into a high-pressure reaction kettle, and adding 1 wt% of Co-Mn/gamma-Al2O3The catalyst is then introduced into the reactor at a flow rate of 0.7L/H2S，H2The adding amount of S is 3 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 400 ℃, and the reaction pressure is 1.0 MPa; the reaction time is 4 h. After the reaction is finished, the catalyst is filtered, the filtrate is washed by acid and then washed by ethanol to remove small molecules, and colorless or slightly yellow liquid, namely the product 1,2, 3-trithioethyl thiopropane, is obtained, the yield is 86 percent, and n isd＝1.6406。
Example 5
(1) Adding 0.5mol of trichloropropane and 1.55mol of mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to reduce the temperature, heating the flask to 85-90 ℃ in a water bath, slowly dropwise adding 0.515mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, gradually changing the solution into colorless when the KOH is nearly dripped, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to be neutral.
(2) And (3) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules.
(3) Putting the obtained triol compound A into a high-pressure reaction kettle, and adding 4 wt% of Ni-W/gamma-Al2O3The catalyst is then introduced into the reactor at a flow rate of 0.8L/H2S，H2The adding amount of S is 5 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 500 ℃, and the reaction pressure is 1.5 MPa; the reaction time is 5 h. After the reaction is finished, the catalyst is filtered, the filtrate is washed by acid and then washed by ethanol to remove small molecules, and colorless or slightly yellow liquid, namely the product 1,2, 3-trithioethyl thiopropane, is obtained, the yield is 85 percent, and n isd＝1.6406。
Example 6
(1) Adding 0.5mol of trichloropropane and 1.5mol of mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to reduce the temperature, heating the flask to 85-90 ℃ in a water bath, slowly dropwise adding 0.52mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, when the KOH is nearly dripped, the solution gradually becomes colorless, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to be neutral.
(2) And (3) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules.
(3) Putting the obtained triol compound A into a high-pressure reaction kettle, and adding 2 wt% of KOH/gamma-Al2O3The catalyst is then introduced into the reactor at a flow rate of 1.1L/H2S，H2The adding amount of S is 4 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 300 ℃, and the reaction pressure is 1.2 MPa; the reaction time was 7 h. After the reaction is finished, the catalyst is filtered, the filtrate is washed by acid and then washed by ethanol to remove small molecules, and colorless or slightly yellow liquid, namely the product 1,2, 3-trithioethyl thiopropane, is obtained, the yield is 85 percent, and n isd＝1.6405。
Example 7
(1) Adding 0.5mol of trichloropropane and 1.49mol of mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to reduce the temperature, heating the flask to 85-90 ℃ in a water bath, slowly dropwise adding 0.5mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, when the KOH is nearly dripped, the solution gradually becomes colorless, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to neutrality.
(2) And (3) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules.
(3) Putting the obtained triol compound A into a high-pressure reaction kettle, adding 12 wt% of silica gel catalyst, and then introducing H at the flow rate of 1.2L/H2S，H2The adding amount of S is 4.5 times of the molar equivalent of the triol compound, the reaction temperature is controlled to be 350 ℃, and the reaction pressure is 0.4 MPa; the reaction time is 8 h. After the reaction is finished, the catalyst is filtered, the filtrate is washed by acid and then washed by ethanol to remove small molecules, and colorless or slightly yellow liquid, namely the product 1,2, 3-trithioethyl thiopropane, is obtained, the yield is 81 percent, and n isd＝1.6402。
Comparative example
(1) Sequentially adding 0.5153mol of trichloropropane and 1.55mol of mercaptoethanol into a four-neck flask, introducing nitrogen to reduce the temperature, heating in a water bath to 85-90 ℃, slowly dropwise adding 0.5256mol of KOH solution with the mass fraction of 50%, wherein mauve appears in the dropwise adding process, when the KOH is nearly completely dropwise added, the solution gradually becomes colorless, then quickly adding the rest KOH, and then adding concentrated HCl to acidify to be neutral;
(2) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules;
(3) reacting the intermediate product with thiourea and hydrochloric acid under heating reflux, adding ammonia water for alkaline hydrolysis after the reaction is finished, adjusting acid, washing with ethanol to remove small molecules to obtain colorless or slightly yellow liquid with yield of 70%, nd＝1.6401。
Claims (10)
1. A preparation method of 1,2, 3-trithio-ethyl-thiopropane is characterized by comprising the following steps: trichloropropane and mercaptoethane are firstly mixedAlcohol reacts to obtain an intermediate triol compound A, and the intermediate triol compound A and the waste gas H2And S is reacted to finally obtain the 1,2, 3-trithio-ethyl-thiopropane. The method comprises the following specific steps:
(1) adding trichloropropane and mercaptoethanol into a four-neck flask in sequence, introducing nitrogen to cool, heating in a water bath to 85-90 ℃, slowly dropwise adding 50% KOH solution in percentage by mass, wherein mauve appears in the dropwise adding process, the solution gradually becomes colorless when the KOH is nearly dripped, quickly adding the rest KOH, and then adding concentrated HCl to acidify to neutrality;
(2) sucking and filtering the mixed solution, removing KCl, standing in a separating funnel for layering to obtain an intermediate triol compound A, and distilling at 70 ℃ to remove small molecules;
(3) putting the obtained intermediate triol compound A into a high-pressure reaction kettle, adding a catalyst, and then introducing H2S, reacting, filtering out the catalyst after the reaction is finished, washing the filtrate with acid, washing the filtrate with ethanol, and removing small molecules to obtain colorless or slightly yellow liquid, namely 1,2, 3-trimercapto ethyl thiopropane;
the catalyst is a molecular sieve catalyst;
the molar ratio of the mercaptoethanol to the trichloropropane in the step (1) is 2.98-3.3, and the molar ratio of the KOH to the trichloropropane is 1.0-1.05.
2. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 1, wherein: the catalyst is gamma-Al2O3And silica gel.
3. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 2, characterized in that: the catalyst is loaded with Ni-Mo, Ni-W, Co-Mn, Co-W, KOH and K2WO4、CsWO4gamma-Al of (2)2O3。
4. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 2, characterized in that: said catalysisThe agent is loaded with K2WO4、CsWO4gamma-Al of (2)2O3。
5. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 4, wherein: the gamma-Al2O3Upper load K2WO4、CsWO4The loading amount of (A) is 1-12% wt.
6. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 4, wherein: the gamma-Al2O3Upper load K2WO4、CsWO4The loading of (A) is 2-5% wt.
7. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 1, wherein: h in the step (3)2The addition amount of S is 3-5 times of the molar equivalent of the triol compound A, H2S is introduced in a gas form, and the flow rate is 0.5L-1.2L/h.
8. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 1, wherein: h in the step (3)2The addition amount of S is 3.2-3.7 times of the molar equivalent of the triol compound A.
9. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 1, wherein: the reaction conditions in the step (3): the reaction temperature is 200 ℃ and 500 ℃, the reaction pressure is 0.2-1.5MP, and the reaction time is 4-9 h.
10. The process for producing 1,2, 3-trimercaptoethylthiopropane according to claim 1, wherein: the reaction conditions in the step (3): the reaction temperature is 200 ℃ and 300 ℃, the reaction pressure is 0.5-0.9MPa, and the reaction time is 6-8 h.
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