CN111909141B - Method for synthesizing TGIC and co-producing ECH from dichloropropanol - Google Patents
Method for synthesizing TGIC and co-producing ECH from dichloropropanol Download PDFInfo
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Abstract
The invention provides a method for synthesizing TGIC and co-producing ECH from dichloropropanol. The method comprises the following steps: (1) adding cyanuric acid, dichloropropanol, quaternary ammonium salt phase transfer catalyst and water in proportion, heating and stirring for stage temperature control reaction, heating and stirring to a certain temperature, keeping the temperature for reaction for a period of time, raising the temperature, keeping the temperature for reaction for a period of time, and then cooling. (2) In the reaction system (1), the vacuum degree is adjusted, liquid caustic soda is dripped while stripping carried water within a certain time, the reaction is carried out for a period of time under heat preservation after the dripping is finished, and then solid salt is removed through plate-and-frame filter pressing. (3) And (3) distilling the filtrate of the step (2) under reduced pressure to remove ECH, and obtaining a crude product TGIC from the residue. And (3) recrystallizing the crude TGIC in an organic solvent for a period of time at low temperature, then carrying out centrifugal separation, washing and drying to obtain a TGIC product. According to the treatment method disclosed by the invention, the cost of TGIC can be effectively reduced, an important organic chemical raw material ECH is produced, and the treatment method is low-carbon and environment-friendly.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and relates to a preparation method of synthetic TGIC; in particular to a preparation method for synthesizing TGIC and coproducing ECH by two steps by using dichloropropanol and cyanuric acid as raw materials.
Background
The TGIC is named Triglycidyl Isocyanurate, 1,3, 5-Triglycidyl-S-triazine triketone and dai-bike in Chinese, and is named 1,3,5-Triglycidyl Isocyanurate in English, is a white crystalline heterocyclic epoxy compound, has active three epoxy groups, can be subjected to high-density crosslinking with hydroxyl in polyester resin, has excellent heat resistance, weather resistance, light resistance, corrosion resistance, chemical resistance and mechanical properties, is mainly used for a curing agent of carboxyl-containing polyester and carboxyl acrylic resin powder coating, and can also be used for manufacturing an electric insulation laminated board, an adhesive, a plastic stabilizer and the like.
At present, there are three main production processes reported in the open. The first is an epoxidation process: TGIC is prepared by reacting 1,3, 5-tris (1' -propenyl) isocyanurate (TAIC) with hydrogen peroxide in the presence of tolyl cyanide. Since the raw material TAIC is very expensive and the preparation of TGIC is economically uncompetitive, it is difficult to achieve the industrial scale as compared with the two-step process and is now rarely adopted. The second is a one-step process: the isocyanuric acid reacts with excessive epichlorohydrin under the action of a catalyst to prepare TGIC. The one-step process was first developed by a research group including drumbeat, central laboratory of Henkel corporation, drumbeat doctor, and the main disadvantages of the one-step process are excessive reaction raw material ratio, low single-pot yield and low yield. The third is a two-step process: the first step is addition reaction, solid phase isocyanuric acid and liquid phase epichlorohydrin are used as catalyst to generate intermediate 1,3,5-tri (1 '-chloro-2' -hydroxy-propyl) isocyanuric acid ester. The second cyclization reaction is to remove 3 HCl molecules of 1,3, 5-tris (1 '-chloro-2' -hydroxy-propyl) isocyanurate with NaOH to produce TGIC.
CN200810155713.X introduces a TGIC production method, which uses two catalysts to carry out addition ring-opening reaction, effectively controls the occurrence of side reaction, and ensures that the product yield and quality are both improved to a certain extent, but the method uses two catalysts, wherein the residue of the catalyst can obviously influence the product quality, and the cyclization reaction has alkaline water coexistence, so that epoxy chloropropane hydrolysis and TGIC ring opening are caused, other by-products are generated, and the production unit consumption is high. Methanol is added as a cosolvent in the step of the synthesis reaction in CN201610361584.4, so that the use amount of ECH is effectively reduced, and the unit consumption and production energy consumption of ECH are reduced.
In order to solve the problems of more side reactions, unstable product quality, high ECH consumption and the like in the traditional synthesis process, the invention provides a preparation method for synthesizing TGIC and co-producing ECH by two steps by taking dichloropropanol and cyanuric acid as raw materials.
Disclosure of Invention
The main object of the present invention is to provide a process for the synthesis of TGIC with co-production of ECH from dichloropropanol. In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a process for the synthesis of TGIC with co-production of ECH from dichloropropanol comprising the steps of: (1) adding cyanuric acid, dichloropropanol, quaternary ammonium salt phase transfer catalyst and water in proportion, heating and stirring for stage temperature control reaction, heating and stirring to a certain temperature, keeping the temperature for reaction for a period of time, raising the temperature, keeping the temperature for reaction for a period of time, and then cooling. (2) In the reaction system (1), the vacuum degree is adjusted, liquid caustic soda is dripped while stripping carried water within a certain time, the reaction is carried out for a period of time under heat preservation after the dripping is finished, and then solid salt is removed through plate-and-frame filter pressing. (3) And (3) distilling the filtrate of the step (2) under reduced pressure to remove ECH, and obtaining a crude product TGIC from the residue. And (3) recrystallizing the crude TGIC in an organic solvent for a period of time at low temperature, then carrying out centrifugal separation, washing and drying to obtain a TGIC product. According to the treatment method disclosed by the invention, the cost of TGIC can be effectively reduced, an important organic chemical raw material ECH is produced, and the treatment method is low-carbon and environment-friendly.
The technical problem to be solved by the invention is to provide a method for synthesizing TGIC and co-producing ECH from dichloropropanol.
The invention aims to provide a method for synthesizing TGIC and coproducing ECH from dichloropropanol, which adopts dichloropropanol as a raw material, can obtain an intermediate 1,3,5-tri (1 '-chloro-2' -hydroxy-propyl) isocyanurate through one-step catalytic reaction, and then performs ring closure with alkali to obtain products TGIC and ECH.
The preparation method of TGIC coproduced with ECH comprises the following steps:
(1) adding dichloropropanol, cyanuric acid, a quaternary ammonium salt phase transfer catalyst and water in a ratio of 12-19: 1, wherein the quaternary ammonium salt phase transfer catalyst accounts for 3-10% of the mass of the cyanuric acid, and the water accounts for 5-12% of the mass of the cyanuric acid, heating, stirring and reacting, and carrying out temperature control reaction at a first stage; and the second stage is temperature controlled reaction.
The quaternary ammonium salt phase transfer catalyst is benzyl trimethyl ammonium chloride (TMBA), benzyl triethyl ammonium chloride (TEBA), tetrabutyl ammonium bromide (TBAB), tetramethyl ammonium chloride, tetrabutyl ammonium chloride, trioctylmethyl ammonium chloride and the like;
the mol ratio of the dichloropropanol to the cyanuric acid is 12-19: 1, preferably 15-17: 1;
the quaternary ammonium salt phase transfer catalyst accounts for 5-12% of the mass of cyanuric acid, and preferably 8-10%;
the water accounts for 2-8% of the mass of the cyanuric acid, and is preferably 3-6%;
the temperature of the first stage of the heating reaction is controlled to be 40-80 ℃, and preferably 50-70 ℃; reacting for 1-6 h, preferably 2-4 h;
the temperature of the second stage of the heating reaction is controlled to be 80-120 ℃, and preferably 90-110 ℃; the reaction is carried out for 0.5 to 3.5 hours, preferably 1 to 2.5 hours.
The reaction equation is:
wherein CA is cyanuric acid and DCP is dichloropropanol.
(2) Adding alkali liquor into the reaction system (1), wherein the mol ratio of the alkali liquor to cyanuric acid is 2: 1-5: 1, controlling the vacuum degree to be-0.070-0.098 MPa, controlling the temperature to be 20-40 ℃, dropwise adding the alkali liquor and stripping the water in a certain time, keeping the temperature for reaction for a period of time after dropwise adding, and removing solid salt by plate-and-frame filter pressing.
The alkali liquor is an aqueous solution of 30-60 wt% of sodium hydroxide and potassium hydroxide, preferably 40-50 wt%;
the molar ratio of the alkali liquor to the cyanuric acid is 2: 1-5: 1, preferably 3: 1-3.5: 1;
the vacuum degree in the dropwise adding stripping stage is-0.055 to-0.1 MPa, and preferably-0.085 to-0.098 MPa; the reaction temperature is 10-60 ℃, and preferably 20-40 ℃; the reaction time is 1-5 h, preferably 2-4 h;
the heat preservation temperature is 20-70 ℃, and preferably 30-50 ℃; the heat preservation time is 1-5 h, preferably 2-4 h.
The reaction equation is:
this step is a ring closure reaction, and the solid salt is removed by pressure filtration to obtain a cyclized solution.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding a solvent into the crude TGIC to perform low-temperature recrystallization for a certain time, and performing centrifugal separation and drying to obtain a TGIC product.
The solvent is methanol, ethanol, isopropanol, toluene, methyl acetate, ethyl acetate and the like;
the temperature is-10 ℃, preferably-5 ℃;
the time is 1-6 h, preferably 2-4 h.
Detailed Description
The following examples illustrate the preparation of the TGIC co-product ECH. The examples are not intended to limit the practical scope of the present invention to the conditions described in the examples.
Example 1
(1) Adding dichloropropanol, cyanuric acid, benzyl trimethyl ammonium chloride and water in a ratio of dichloropropanol to cyanuric acid, wherein the molar ratio of dichloropropanol to cyanuric acid is 12:1, the mass of benzyl trimethyl ammonium chloride is 8% of the mass of cyanuric acid, the mass of water is 8% of the mass of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 70 ℃ in the first stage to react for 3 hours; the temperature of the second stage is controlled at 80 ℃, and the reaction is carried out for 2 h.
(2) Adding 40 wt% of sodium hydroxide alkali liquor into the reaction system (1), controlling the mol ratio of the alkali liquor to cyanuric acid to be 5:1, controlling the vacuum degree to be 0.1MPa and the temperature to be 10 ℃, dropwise adding the liquid alkali while stripping the entrained water, finishing dropwise adding for 4h, keeping the temperature at 70 ℃ for reaction for 3h, and then removing solid salt by plate-and-frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding toluene into the crude TGIC, recrystallizing at-5 ℃ for 3h, centrifuging, and drying to obtain a TGIC product.
Example 2
(1) Adding dichloropropanol, cyanuric acid, benzyl trimethyl ammonium chloride and water according to a proportion, wherein the molar ratio of dichloropropanol to cyanuric acid is 17:1, the mass of benzyl trimethyl ammonium chloride is 5% of that of cyanuric acid, the mass of water is 3% of that of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 50 ℃ in the first stage for 4 hours; the temperature of the second stage is controlled at 90 ℃ and the reaction lasts for 2.5 h.
(2) Adding 50 wt% of sodium hydroxide alkali liquor into the reaction system (1), wherein the mol ratio of the alkali liquor to cyanuric acid is 4:1, controlling the vacuum degree to be 0.055MPa and the temperature to be 60 ℃, adding the liquid alkali while stripping the entrained water, finishing the adding after 2h, keeping the temperature at 40 ℃ for reaction for 2h, and then removing the solid salt by plate-and-frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding toluene into the crude TGIC, recrystallizing at 0 ℃ for 4h, centrifuging, and drying to obtain a TGIC product.
Example 3
(1) Adding dichloropropanol, cyanuric acid, benzyltriethylammonium chloride and water in a ratio of dichloropropanol to cyanuric acid, wherein the molar ratio of dichloropropanol to cyanuric acid is 17:1, the benzyltriethylammonium chloride accounts for 12% of the mass of cyanuric acid, the water accounts for 8% of the mass of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 60 ℃ in the first stage for 2 hours; the temperature of the second stage is controlled at 110 ℃, and the reaction is carried out for 1 h.
(2) Adding 30 wt% of potassium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 3:1, controlling the vacuum degree to be 0.085MPa and the temperature to be 40 ℃, dropwise adding the liquid alkali while stripping the entrained water, finishing dropwise adding after 3h, carrying out heat preservation reaction for 3h at the temperature of 30 ℃, and then removing the solid salt by adopting plate-and-frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding methanol into the crude TGIC, recrystallizing at 5 ℃ for 6h, centrifuging, and drying to obtain a TGIC product.
Example 4
(1) Adding dichloropropanol, cyanuric acid, tetramethylammonium chloride and water in a ratio of dichloropropanol to cyanuric acid of 16:1, wherein the molar ratio of tetramethylammonium chloride to cyanuric acid is 8% by mass, the molar ratio of water to cyanuric acid is 3% by mass, heating, stirring and reacting, and controlling the temperature at 80 ℃ in the first stage for 1 h; the temperature of the second stage is controlled at 90 ℃ and the reaction lasts for 1 h.
(2) Adding 45 wt% of sodium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 4:1, controlling the vacuum degree to be 0.080MPa and the temperature to be 45 ℃, adding the liquid alkali while stripping the water, finishing the adding for 1h, keeping the temperature at 50 ℃ for reaction for 2h, and then removing the solid salt by plate and frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding ethyl acetate into the crude TGIC, recrystallizing at-10 ℃ for 1h, centrifuging, and drying to obtain a TGIC product.
Example 5
(1) Adding dichloropropanol, cyanuric acid, tetrabutylammonium bromide and water in proportion, wherein the molar ratio of dichloropropanol to cyanuric acid is 19:1, the mass of tetrabutylammonium bromide is 9% of the mass of cyanuric acid, the mass of water is 6% of the mass of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 70 ℃ in the first stage for 2 hours; the temperature of the second stage is controlled at 100 ℃ and the reaction lasts for 2 hours.
(2) Adding 50 wt% of potassium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 3.5:1, controlling the vacuum degree to be 0.1MPa and the temperature to be 30 ℃, dropwise adding liquid alkali while stripping water, finishing dropwise adding within 3h, carrying out heat preservation reaction at 40 ℃ for 1h, and then removing solid salt by adopting plate and frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and a crude product TGIC, adding ethyl acetate into the crude product TGIC, recrystallizing at 0 ℃ for 3 hours, and drying after centrifugal separation to obtain a TGIC product.
Example 6
(1) Adding dichloropropanol, cyanuric acid, tetrabutylammonium bromide and water in proportion, wherein the molar ratio of dichloropropanol to cyanuric acid is 15:1, the mass of tetrabutylammonium bromide is 10% of the mass of cyanuric acid, the mass of water is 5% of the mass of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 60 ℃ in the first stage for 3 hours; the temperature of the second stage is controlled at 90 ℃ and the reaction lasts for 0.5 h.
(2) Adding 40 wt% of potassium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 5:1, controlling the vacuum degree to be-0.1 MPa and the temperature to be 20 ℃, adding the liquid alkali while stripping the entrained water, finishing the adding for 4h, keeping the temperature at 20 ℃ and reacting for 5h, and then removing solid salt by adopting plate-and-frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding isopropanol into the crude TGIC, recrystallizing at 10 ℃ for 6h, centrifuging, and drying to obtain a TGIC product.
Example 7
(1) Adding dichloropropanol, cyanuric acid, tetrabutyl ammonium chloride and water in a ratio of 18:1, wherein the mol ratio of dichloropropanol to cyanuric acid is 5% of the mass of the tetrabutyl ammonium chloride and the mass ratio of water is 2% of the mass of the cyanuric acid, heating, stirring and reacting, and controlling the temperature at 40 ℃ in the first stage for 6 hours; the temperature of the second stage is controlled at 120 ℃ and the reaction lasts for 0.5 h.
(2) Adding 60 wt% of potassium hydroxide alkali liquor into the reaction system (1), controlling the molar ratio of the alkali liquor to cyanuric acid to be 2:1, controlling the vacuum degree to be 0.1MPa and the temperature to be 30 ℃, dropwise adding the liquid alkali while stripping the entrained water, finishing dropwise adding for 2h, keeping the temperature at 50 ℃ for reaction for 2h, and then removing solid salt by plate-and-frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding ethanol into the crude TGIC, recrystallizing at-5 ℃ for 2h, centrifuging, and drying to obtain a TGIC product.
Example 8
(1) Adding dichloropropanol, cyanuric acid, tetrabutyl ammonium chloride and water in a ratio of 15:1, wherein the mol ratio of dichloropropanol to cyanuric acid is 9% of the mass of the tetrabutyl ammonium chloride, and the mol ratio of water is 6% of the mass of the cyanuric acid, heating, stirring and reacting, and controlling the temperature at 50 ℃ in the first stage for 4 hours; the temperature of the second stage is controlled at 95 ℃, and the reaction is carried out for 3.5 h.
(2) Adding 60 wt% of sodium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 3:1, controlling the vacuum degree to be 0.098MPa, controlling the temperature to be 35 ℃, adding the liquid alkali while stripping the entrained water, finishing the adding for 1h, keeping the temperature at 45 ℃ for reaction for 4h, and then removing the solid salt by plate and frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding isopropanol into the crude TGIC, recrystallizing at 0 ℃ for 4h, centrifuging, and drying to obtain a TGIC product.
Example 9
(1) Adding dichloropropanol, cyanuric acid, trioctylmethylammonium chloride and water in a ratio of dichloropropanol to cyanuric acid, wherein the molar ratio of dichloropropanol to cyanuric acid is 13:1, the amount of trioctylmethylammonium chloride is 7% of the mass of cyanuric acid, and the amount of water is 5% of the mass of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 50 ℃ in the first stage to react for 3 hours; the temperature of the second stage is controlled at 95 ℃, and the reaction is carried out for 2 h.
(2) Adding 48 wt% of potassium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 4:1, controlling the vacuum degree to be 0.099MPa, controlling the temperature to be 35 ℃, adding liquid alkali while stripping water, finishing adding dropwise for 2h, keeping the temperature at 50 ℃ for reaction for 2h, and then removing solid salt by plate and frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding methyl acetate into the crude TGIC, recrystallizing at-5 ℃ for 3h, centrifuging, and drying to obtain a TGIC product.
Example 10
(1) Adding dichloropropanol, cyanuric acid, benzyl trimethyl ammonium chloride and water in a ratio of dichloropropanol to cyanuric acid, wherein the molar ratio of dichloropropanol to cyanuric acid is 16.5:1, the mass of benzyl trimethyl ammonium chloride is 10% of the mass of cyanuric acid, the mass of water is 6% of cyanuric acid, heating, stirring and reacting, and controlling the temperature at 70 ℃ in the first stage to react for 1 hour; the temperature of the second stage is controlled at 100 ℃, and the reaction is carried out for 2.5 h.
(2) Adding 30 wt% of sodium hydroxide alkali liquor into the reaction system (1), wherein the molar ratio of the alkali liquor to cyanuric acid is 3.5:1, controlling the vacuum degree to be 0.1MPa, the temperature to be 25 ℃, adding the liquid alkali while stripping the entrained water, finishing the adding after 3h, keeping the temperature to react for 2h at 45 ℃, and then removing the solid salt by adopting plate-and-frame filter pressing.
(3) And distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding methanol into the crude TGIC, recrystallizing at-10 ℃ for 2h, centrifuging, and drying to obtain a TGIC product.
The following table is the analytical data for the TGIC products obtained in the above examples:
Claims (9)
1. a preparation method for synthesizing TGIC and co-producing ECH comprises the following steps: the method is characterized by comprising the following steps:
(1) adding dichloropropanol, cyanuric acid, a quaternary ammonium salt phase transfer catalyst and water in proportion, heating and stirring for reaction, and carrying out temperature control reaction at the first stage; the second stage of temperature control reaction; the mol ratio of the dichloropropanol to the cyanuric acid is 12-19: 1; the quaternary ammonium salt phase transfer catalyst accounts for 5-12% of the mass of cyanuric acid; the water accounts for 2-8% of the mass of the cyanuric acid; the temperature of the first stage of the heating reaction is controlled to be 40-80 ℃; reacting for 1-6 h; the quaternary ammonium salt phase transfer catalyst is benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride and trioctylmethylammonium chloride;
(2) adding alkali liquor into the reaction system in the step (1), controlling the vacuum degree and the temperature, dropwise adding the alkali liquor while stripping the entrained water within a certain time, preserving the temperature after dropwise adding for a period of time, and then removing solid salt by plate-and-frame filter pressing; the temperature of the second stage of the heating reaction is controlled to be 80-120 ℃; reacting for 0.5-3.5 h, wherein the alkali liquor is an aqueous solution of 30-60 wt% of sodium hydroxide and potassium hydroxide, and the molar ratio of the alkali liquor to cyanuric acid is 2: 1-5: 1; the vacuum degree in the dropwise adding stripping stage is-0.055 to-0.1 MPa; the reaction temperature is 10-60 ℃; the reaction time is 1-5 h; the heat preservation temperature is 20-70 ℃; the heat preservation time is 1-5 h;
(3) distilling the cyclized solution under reduced pressure to obtain ECH and crude TGIC, adding a solvent into the crude TGIC to perform low-temperature recrystallization for a certain time, performing centrifugal separation and drying to obtain a TGIC product, wherein the low-temperature recrystallization temperature is-10 ℃; the time is 1-6 h.
2. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: the method is characterized in that the molar ratio of dichloropropanol to cyanuric acid is 15-17: 1; the quaternary ammonium salt phase transfer catalyst accounts for 8-10% of the mass of cyanuric acid; the water accounts for 3-6% of the mass of the cyanuric acid.
3. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: the method is characterized in that the temperature of the first stage of the heating reaction is controlled to be 50-70 ℃; and reacting for 2-4 h.
4. The process of preparation of synthetic TGIC with co-production of ECH of claim 1: the method is characterized in that the temperature of the second stage of the heating reaction is controlled at 90-110 ℃; reacting for 1-2.5 h.
5. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: the method is characterized in that the alkali liquor is an aqueous solution of 40-50 wt% of sodium hydroxide and potassium hydroxide.
6. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: the method is characterized in that the molar ratio of the alkali liquor to the cyanuric acid is 3: 1-3.5: 1.
7. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: it is characterized in that the vacuum degree in the dropwise adding and stripping stage is-0.085 to-0.098 MPa; the reaction temperature is 20-40 ℃; the reaction time is 2-4 h; the heat preservation temperature is 30-50 ℃; and keeping the temperature for 2-4 h.
8. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: the method is characterized in that the solvents are methanol, ethanol, isopropanol, toluene, methyl acetate and ethyl acetate.
9. The method of claim 1 for the preparation of synthetic TGIC co-produced ECH: it is characterized in that the temperature of low-temperature recrystallization is-5 to 5 ℃; the time is 2-4 h.
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