CN108164428B - Preparation method of tris (2-chloroethyl) amine hydrochloride - Google Patents
Preparation method of tris (2-chloroethyl) amine hydrochloride Download PDFInfo
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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Abstract
The invention discloses a preparation method of tris (2-chloroethyl) amine hydrochloride, which specifically comprises the steps of taking triethanolamine as a raw material, taking Lewis acid as a catalyst, and taking hydrogen chloride as a chlorination reagent to carry out substitution reaction to prepare the tris (2-chloroethyl) amine hydrochloride. The method of the invention produces hydrogen chloride as a byproduct of a company, and has easily obtained raw materials and quick reaction; the product yield and purity are high; the byproduct hydrogen chloride is used as a chlorinated reagent to replace thionyl chloride, thereby avoiding the generation of polluting gases such as sulfur dioxide and the like and greatly reducing the environmental pollution.
Description
Technical Field
The invention belongs to the field of fine chemicals, and particularly relates to a preparation method of tris (2-chloroethyl) amine hydrochloride.
Background
Tris (2-chloroethyl) amine hydrochloride is an important intermediate raw material for producing pesticides, medicines and oligomeric surfactants. The C-Cl bond in the molecular structure has stronger polarity, and can generate chemical reaction with a plurality of kinds of nucleophiles to generate a plurality of kinds of compounds.
The tris (2-chloroethyl) amine hydrochloride is mainly prepared by synthesizing triethanolamine serving as a raw material and thionyl chloride serving as a chlorination reagent. However, the price of thionyl chloride is relatively high, which results in increased raw material cost, and the byproduct is a pollutant gas, namely sulfur dioxide, which has great pollution and can cause environmental pollution.
At present, hydrogen chloride serving as a byproduct of hydrogen chloride manufacturers is a difficult problem, but the process for preparing tris (2-chloroethyl) amine hydrochloride by using hydrogen chloride is not reported at present, so that the process for producing tris (2-chloroethyl) amine hydrochloride by using hydrogen chloride as a raw material can relieve the defects of the original process and provides an idea for developing high-added-value products of the byproduct hydrogen chloride manufacturers, the regeneration and utilization of the byproduct hydrogen chloride can be effectively realized, and the economic benefit and the social benefit are huge.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention researches a preparation method for generating high-purity tris (2-chloroethyl) amine hydrochloride by using industrial byproduct hydrogen chloride as a chlorination reagent, lewis acid as a catalyst and triethanolamine as a raw material through chlorination reaction.
The invention adopts the following scheme to prepare:
a preparation method of tris (2-chloroethyl) amine hydrochloride is prepared by the following process:
the preparation method specifically comprises the following steps:
(1) adding triethanolamine into a three-mouth reaction bottle, stirring, connecting a buffer bottle filled with an absorption solution to the outlet end, starting introducing hydrogen chloride at room temperature, and stopping introducing hydrogen chloride gas when the pH value of the system is 2-3;
(2) adding Lewis acid into the container in the step (1), heating, introducing hydrogen chloride again, reacting while distilling, and removing generated water by evaporation;
(3) and (3) stopping heating after the reaction in the step (2) is finished, stopping introducing hydrogen chloride, cooling to room temperature, adding absolute ethyl alcohol, stirring, performing suction filtration to obtain a filter cake, and drying to obtain a finished product of the tris (2-chloroethyl) amine hydrochloride.
Preferably, the following components: when the triethanolamine is 1mol, the flow rate of the hydrogen chloride gas is 300-500 mL/min, and the aeration time is 45-75 min.
Preferably, the lewis acid in (1) above is aluminum sulfate, zinc sulfate, copper sulfate or iron sulfate.
Preferably, the mass ratio of the lewis acid in the above (2) to the triethanolamine in the step (1) is 0.05-0.15: 1.
Preferably, the absorption solution in step (1) is 0.1-2M sodium hydroxide solution.
Preferably, the reaction temperature in the step (2) is 150 to 170 ℃, and the reaction time of the distillation while the reaction is performed is 5 to 8 hours. .
Preferably, the hydrogen chloride gas flow rate described in (2) above: when the triethanolamine is 1mol, the flow rate of the hydrogen chloride gas is 500-800 mL/min.
Preferably, the mass ratio of the absolute ethanol to the triethanolamine described in (3) is 0.2 to 0.4: 1.
Preferably, the drying in the step (3) adopts vacuum drying at 50-60 ℃.
Advantageous effects
The research of the invention provides a new method for preparing the tris (2-chloroethyl) amine hydrochloride. The method has the advantages of simple operation, easily obtained raw materials and low cost; the purity of the product can reach 99 percent; the byproduct hydrogen chloride is used as a chlorinated reagent to replace thionyl chloride, thereby avoiding the generation of polluting gases such as sulfur dioxide and the like and greatly reducing the environmental pollution. The invention provides a thought for the development of high value-added products of by-product hydrogen chloride manufacturers, effectively realizes the recycling of the by-product hydrogen chloride, and brings huge economic and social benefits.
Detailed Description
The present invention will be further described with reference to examples, but the following description is only for the purpose of explaining the present invention and does not limit the contents thereof.
Example 1
The preparation method of the tris (2-chloroethyl) amine hydrochloride comprises the following steps:
the specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 1M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, controlling the gas flow to be 500mL/min, controlling the gas introduction time to be 45min, controlling the pH value to be about 3, and stopping introducing gas;
(2) 7.45g of aluminum sulfate was added, heating was started, the temperature was raised to 150 ℃ and hydrogen chloride was introduced again at a gas flow rate of 500 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 8 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 30g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 219g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 90.8%, and the GC purity is 99.0% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Example 2
The preparation method of the tris (2-chloroethyl) amine hydrochloride comprises the following steps:
the specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 1M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, controlling the gas flow to be 300mL/min, the gas introduction time to be 75min, controlling the pH value to be about 2, and stopping introducing gas;
(2) 7.45g of zinc sulphate was added, heating was started, the temperature was raised to 150 ℃ and hydrogen chloride was introduced again at a gas flow of 800 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 6.5 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 30g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 220g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 91.3%, and the GC purity is 99.1% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Example 3
The preparation method of the tris (2-chloroethyl) amine hydrochloride comprises the following steps:
the specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 0.1M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, wherein the gas flow is 400mL/min, the gas introduction time is 55min, the pH value is about 3, and stopping introducing gas;
(2) 14.9g of zinc sulphate were added, heating was started, the temperature was raised to 170 ℃ and hydrogen chloride was introduced again at a gas flow of 600 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 5 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 45g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 215g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 89.2%, and the GC purity is 99.3% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Example 4
The preparation method of the tris (2-chloroethyl) amine hydrochloride comprises the following steps:
the specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 0.1M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, wherein the gas flow is 500mL/min, the gas introduction time is 45min, the pH value is about 2, and stopping introducing gas;
(2) 14.9g of copper sulfate was added, heating was started, the temperature was raised to 160 ℃ and hydrogen chloride was introduced again at a gas flow rate of 600 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 8 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 45g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 213g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 88.4%, and the GC purity is 99.3% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Example 5
The preparation method of the tris (2-chloroethyl) amine hydrochloride comprises the following steps:
the specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 2M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, controlling the gas flow to be 500mL/min, controlling the gas introduction time to be 45min, controlling the pH value to be about 3, and stopping introducing gas;
(2) 14.9g of cerium sulfate were added, heating was started, the temperature was raised to 170 ℃ and hydrogen chloride was introduced again at a gas flow rate of 800 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 6 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 60g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 212g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 88.0%, and the GC purity is 99.4% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Example 6
The preparation method of the tris (2-chloroethyl) amine hydrochloride comprises the following steps:
the specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 1M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, controlling the gas flow to be 500mL/min, controlling the gas introduction time to be 45min, controlling the pH value to be about 2, and stopping introducing gas;
(2) 7.9g of zinc sulphate was added, heating was started, the temperature was raised to 160 ℃ and hydrogen chloride was introduced again at a gas flow rate of 600 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 8 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 45g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 216g of solid, namely a finished product of tris (2-chloroethyl) amine hydrochloride, wherein the yield is 89.6%, and the GC purity is 99.0% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Example 7
The specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 1M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, controlling the gas flow to be 500mL/min, controlling the gas introduction time to be 45min, controlling the pH value to be about 2, and stopping introducing gas;
(2) 6.0g of zinc sulphate was added, heating was started, the temperature was raised to 140 ℃ and hydrogen chloride was introduced again at a gas flow rate of 900 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 10 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 50g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 195g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 80.9%, and the GC purity is 90.0% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Comparative example 1
The specific operation steps are as follows:
(1) adding 149g of triethanolamine into a three-mouth reaction bottle, starting stirring, connecting an outlet end with a buffer bottle, absorbing by using 2M sodium hydroxide solution, starting introducing hydrogen chloride at room temperature, controlling the gas flow to be 500mL/min, controlling the gas introduction time to be 45min, controlling the pH value to be about 3, and stopping introducing gas;
(2) heating is started, the temperature is raised to 170 ℃, hydrogen chloride is introduced again, and the gas flow is 800 mL/min. The reaction and distillation were carried out simultaneously, and the water produced was immediately distilled off. After 8 hours of reaction, heating was stopped and aeration was stopped. Cooling to room temperature, adding 45g of absolute ethyl alcohol, stirring, carrying out suction filtration to obtain a filter cake, carrying out vacuum drying at 50-60 ℃ for 5 hours, collecting 63g of solid, namely the finished product of the tris (2-chloroethyl) amine hydrochloride, wherein the yield is 26.1%, and the GC purity is 83.0% (SE-54 chromatographic column, detector, hydrogen flame ionization detector, column temperature is 50 ℃, detection chamber temperature is 250 ℃, vaporization chamber temperature is 250 ℃, carrier gas (N2) is 30ml/min, split ratio is 1: 60, hydrogen is 30ml/min, air is 300ml/min, and the sample introduction amount is 1 muL).
Claims (8)
1. A preparation method of tris (2-chloroethyl) amine hydrochloride is characterized by comprising the following steps:
the preparation method specifically comprises the following steps:
(1) adding triethanolamine into a three-mouth reaction bottle, stirring, connecting a buffer bottle filled with an absorption solution to the outlet end, starting introducing hydrogen chloride at room temperature, and stopping introducing hydrogen chloride gas when the pH value of the system is 2-3;
(2) adding Lewis acid into the container in the step (1), heating, introducing hydrogen chloride again, reacting while distilling, and removing generated water by evaporation; the Lewis acid is aluminum sulfate, zinc sulfate or copper sulfate.
(3) And (3) stopping heating after the reaction in the step (2) is finished, stopping introducing hydrogen chloride, cooling to room temperature, adding absolute ethyl alcohol, stirring, performing suction filtration to obtain a filter cake, and drying to obtain the tris (2-chloroethyl) amine hydrochloride.
2. The method according to claim 1, wherein the hydrogen chloride gas flow rate in step (1): when the triethanolamine is 1mol, the flow rate of the hydrogen chloride gas is 300-500 mL/min, and the aeration time is 45-75 min.
3. The preparation method of claim 1, wherein the mass ratio of the Lewis acid in the step (2) to the triethanolamine in the step (1) is 0.05-0.15: 1.
4. The method according to claim 1, wherein the absorbing solution in the step (1) is a 0.1-2M sodium hydroxide solution.
5. The method according to claim 1, wherein the reaction temperature in the step (2) is 150 to 170 ℃, and the reaction time of the distillation while the reaction is carried out is 5 to 8 hours.
6. The method according to claim 1, wherein the hydrogen chloride gas flow rate in step (2): when the triethanolamine is 1mol, the flow rate of the hydrogen chloride gas is 500-800 mL/min.
7. The preparation method according to claim 1, wherein the mass ratio of the absolute ethanol to the triethanolamine in the step (3) is 0.2-0.4: 1.
8. The preparation method according to claim 1, wherein the drying in the step (3) is performed by vacuum drying at 50-60 ℃.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57179135A (en) * | 1981-04-28 | 1982-11-04 | Mitsui Toatsu Chem Inc | Preparation of chloroalkylamine hydrochlorides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133247A (en) * | 1980-03-21 | 1981-10-19 | Teijin Ltd | Production of 2-chloroethylamine hydrochloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57179135A (en) * | 1981-04-28 | 1982-11-04 | Mitsui Toatsu Chem Inc | Preparation of chloroalkylamine hydrochlorides |
Non-Patent Citations (1)
| Title |
|---|
| Reversible encapsulation of a nitrate guest via hydrogen-bonded selfassembled capsule formation by a flexible tripodal receptor in polar solvent through dynamic self-assembly;Shih-Sheng Sun等;《RSC Advances》;20121231;第2卷;第9504页左栏Scheme 1 * |
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