CN107176903B - Method for synthesizing 3-chloro-1, 2-propanediol - Google Patents
Method for synthesizing 3-chloro-1, 2-propanediol Download PDFInfo
- Publication number
- CN107176903B CN107176903B CN201710502448.7A CN201710502448A CN107176903B CN 107176903 B CN107176903 B CN 107176903B CN 201710502448 A CN201710502448 A CN 201710502448A CN 107176903 B CN107176903 B CN 107176903B
- Authority
- CN
- China
- Prior art keywords
- reaction
- materials
- percent
- chloro
- reaction kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 3-chloro-1, 2-propanediol by catalytic hydrolysis, which takes sulfamic acid as a catalyst, water as a reaction medium and epichlorohydrin as a raw material to carry out catalytic hydrolysis reaction. The invention has low temperature requirement in the reaction process, high conversion rate, less harmful impurities, no corrosion to production equipment, high product purity of over 99.5 percent and no color change after long-term storage.
Description
Technical Field
The invention belongs to the field of catalytic synthesis of fine chemicals, and particularly relates to a method for synthesizing 3-chloro-1, 2-propanediol by using epoxy chloropropane as a raw material.
Technical Field
3-chloro-1, 2-propylene glycol is also called chloro-glycerol, is an intermediate for synthesizing substances such as guaifenesin, a plasticizer, a surfactant, a dye and the like, is an important structural unit for synthesizing X-CT nonionic iodine series contrast agents, and is an irreplaceable raw material. The preparation method commonly used at present has the following problems:
(1) the 3-chloro-1, 2-propanediol is synthesized by catalytic hydrolysis of epichlorohydrin as a raw material and deionized water as a reaction medium, and the catalyst used is sulfuric acid, p-toluenesulfonic acid, organic acid, strong-acid ion exchange resin and the like. The method is the main industrial production method at present, and has the disadvantages of low conversion rate, product purity of only about 99 percent, poor stability of the prepared product and easy color change; the problem which is not easy to solve is that a series of complex series reactions can occur in the hydrolysis process and harmful substances such as 1, 3-dichloro-2-propanol, secondary condensate, high-boiling-point substance and the like are generated, wherein the high-boiling-point substance which is difficult to treat is more than or equal to 10 percent, in addition, the used acid catalyst has corrosion side effect on equipment and is easy to introduce harmful metal ions into the product.
(2) The production process has high requirement on equipment, complicated operation steps, is not suitable for industrial large-scale production and is rarely adopted in the actual production of enterprises.
(3) As 3-chloro-1, 2-propanediol has large viscosity, high boiling point (bp =213 ℃) and is extremely easy to absorb moisture, in the existing synthetic method, an anhydrous product is generally difficult to form and is difficult to store, once moisture is absorbed, when the water content is high, 3-chloro-1, 2-propanediol can be hydrolyzed to form glycerol and hydrochloric acid at room temperature, and the existence of hydrochloric acid can certainly cause the occurrence of a series reaction, so that the water content of the product is required to be controlled below 0.1%.
The invention provides a preparation method of 3-chloro-1, 2-propanediol, which adopts non-oxygen type non-corrosive sulfamic acid as a catalyst, takes epoxy chloropropane as a raw material and deionized water as a reaction medium to synthesize and prepare the 3-chloro-1, 2-propanediol.
Disclosure of Invention
In order to achieve the purpose, the technical solution adopted by the invention is as follows: a method of synthesizing 3-chloro-1, 2-propanediol comprising the steps of:
(1) adding deionized water and a catalyst into a reaction kettle, uniformly stirring, heating to 60 ℃, dropwise adding epoxy chloropropane, and controlling the temperature of materials in the reaction kettle not to exceed 80 ℃ in the whole dropwise adding process;
(2) after the epoxy chloropropane is dripped, raising the temperature of the materials in the reaction kettle to 85-95 ℃, continuing to react for 2-4 hours, and when the gas chromatograph does not detect the epoxy chloropropane, finishing the reaction, and reducing the temperature of the materials in the reaction kettle to 50 ℃;
(3) and (3) adding a 30% NaOH solution into the reaction solution until the pH value is 6-8, dehydrating, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa after dehydration. And after removing the front fraction, starting to collect the positive fraction to obtain the product 3-chloro-1, 2-propanediol.
Preferably, the catalyst in the step (1) is sulfamic acid, and the dosage of the sulfamic acid is 0.4-1% of the mass of the epichlorohydrin.
Preferably, the mass ratio of the epichlorohydrin to the deionized water in the step (1) is 1: 1.2 to 1.8.
Preferably, the reaction temperature in the step (2) is 85-90 ℃, and the reaction time is 2-3 h.
Preferably, the material is neutralized to pH 7 by adding NaOH solution in step (3).
The invention adopts sulfamic acid as a catalyst, and is different from catalyst acid used in other hydrolysis reactions, the sulfamic acid is non-oxygen, so that side reaction can not be promoted in the hydrolysis reaction, and the generation of high-boiling-point substances is reduced; meanwhile, the sulfamic acid is non-corrosive, and cannot corrode equipment in the reaction process, so that the production equipment is abraded. The determination shows that the purity of the 3-chloro-1, 2-propanediol synthesized by the method is up to more than 99.5 percent, the conversion rate is up to more than 90 percent, the content of high-boiling-point substances is lower than 9 percent, and the water content of the obtained product is lower than 0.1 percent. And the product does not change color after being placed for six months.
Detailed Description
The present invention will be described in further detail below with reference to embodiments.
Example 1
Adding 700Kg of deionized water and 2.5Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 85 ℃ after dropwise adding is finished, continuing to react for 2 hours, analyzing the epoxy chloropropane by gas chromatography, finishing the reaction when the content of the epoxy chloropropane is 0, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% of NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.5 percent, the conversion rate is 90 percent, the content of high-boiling-point substances is 8.8 percent and the water content is 0.09 percent as determined by a gas chromatograph.
Example 2
Adding 700Kg of deionized water and 2.5Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 90 ℃ after dropwise adding is finished, continuing to react for 2.5 hours, analyzing the epoxy chloropropane by gas chromatography, when the content of the epoxy chloropropane is 0, finishing the reaction, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% of NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.6 percent, the conversion rate is 91 percent, the content of high-boiling-point substances is 8 percent and the water content is 0.09 percent as determined by a gas chromatograph.
Example 3
Adding 700Kg of deionized water and 3Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 90 ℃ after the dropwise adding is finished, continuing to react for 3 hours, analyzing the epoxy chloropropane by gas chromatography, finishing the reaction when the content of the epoxy chloropropane is 0, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.8 percent, the conversion rate is 93 percent, the content of high-boiling-point substances is 7.8 percent and the water content is 0.08 percent as determined by a gas chromatograph.
Example 4
Adding 700Kg of deionized water and 3Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 90 ℃ after the dropwise adding is finished, continuing to react for 3.5 hours, analyzing the epoxy chloropropane by gas chromatography, when the content of the epoxy chloropropane is 0, finishing the reaction, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% of NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.8 percent, the conversion rate is 92 percent, the content of high-boiling-point substances is 7.5 percent and the water content is 0.08 percent as determined by a gas chromatograph.
Example 5
Adding 750Kg of deionized water and 3.5Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 90 ℃ after dropwise adding is finished, continuing to react for 3.5 hours, analyzing the epoxy chloropropane by gas chromatography, when the content of the epoxy chloropropane is 0, finishing the reaction, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% of NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.63 percent, the conversion rate is 91 percent, the content of high-boiling-point substances is 8 percent and the content of water is 0.08 percent as determined by a gas chromatograph.
Example 6
Adding 750Kg of deionized water and 4Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 95 ℃ after the dropwise adding is finished, continuing to react for 4 hours, analyzing the epoxy chloropropane by gas chromatography, finishing the reaction when the content of the epoxy chloropropane is 0, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.7 percent, the conversion rate is 91 percent, the content of high-boiling-point substances is 8 percent and the water content is 0.09 percent as determined by a gas chromatograph.
Example 7
Adding 750Kg of deionized water and 5Kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, starting to gradually dropwise add 500Kg of epoxy chloropropane, controlling the temperature of materials in the reaction kettle to be lower than 80 ℃ in the whole dropwise adding process because the reaction is an exothermic reaction, heating to 95 ℃ after the dropwise adding is finished, continuing to react for 4 hours, analyzing the epoxy chloropropane by gas chromatography, finishing the reaction when the content of the epoxy chloropropane is 0, cooling to 50 ℃, neutralizing the materials in the reaction kettle by using 30% NaOH aqueous solution to ensure that the pH value is 7, starting to evaporate water in the materials, and then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa. And after removing the front fraction, collecting the positive fraction to obtain the product 3-chloro-1, 2-propanediol, wherein the purity of the product is 99.6 percent, the conversion rate is 92 percent, the content of high-boiling-point substances is 8.5 percent and the water content is 0.09 percent as determined by a gas chromatograph.
Claims (1)
1. A method for synthesizing 3-chloro-1, 2-propanediol, comprising the steps of:
(1) adding 700kg of deionized water and 3kg of sulfamic acid into a reaction kettle, uniformly stirring, heating to 60 ℃, then dropwise adding 500kg of epoxy chloropropane, and controlling the temperature of materials in the reaction kettle not to exceed 80 ℃ in the whole dropwise adding process;
(2) after the dropwise addition of the epichlorohydrin is finished, raising the temperature of the materials in the reaction kettle to 90 ℃, continuing to react for 3 hours, analyzing the epichlorohydrin by using gas chromatography, and when the epichlorohydrin is not detected in the materials, finishing the reaction, and lowering the temperature of the materials in the reaction kettle to 50 ℃;
(3) and (3) adding a 30% NaOH solution into the material obtained in the step (2) until the pH value is 7, then beginning to evaporate water in the material, then carrying out reduced pressure distillation under the vacuum degree of-0.1 MPa, and collecting fractions to obtain the product 3-chloro-1, 2-propanediol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710502448.7A CN107176903B (en) | 2017-06-27 | 2017-06-27 | Method for synthesizing 3-chloro-1, 2-propanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710502448.7A CN107176903B (en) | 2017-06-27 | 2017-06-27 | Method for synthesizing 3-chloro-1, 2-propanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107176903A CN107176903A (en) | 2017-09-19 |
| CN107176903B true CN107176903B (en) | 2020-12-11 |
Family
ID=59844785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710502448.7A Active CN107176903B (en) | 2017-06-27 | 2017-06-27 | Method for synthesizing 3-chloro-1, 2-propanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107176903B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299952B (en) * | 2020-11-05 | 2023-08-29 | 嘉兴润博化工科技有限公司 | Method for producing 3-chloro-1, 2-propanediol by using acetic anhydride modified graphene oxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1233377B (en) * | 1965-02-13 | 1967-02-02 | Raschig Gmbh Dr F | Method for purifying 3-chloro-propanediol- (1, 2) |
| CN101161632A (en) * | 2006-10-10 | 2008-04-16 | 中科院嘉兴中心应用化学分中心 | Preparation method of polyhydric alcohol amine |
| CN101759577A (en) * | 2008-12-25 | 2010-06-30 | 浙江医药股份有限公司新昌制药厂 | Synthesis method of (R)-moprolol |
| CN101928202A (en) * | 2010-01-16 | 2010-12-29 | 张中法 | Production method of high-purity 3-chloro-1, 2-propanediol |
| CN102229523A (en) * | 2011-05-25 | 2011-11-02 | 张中法 | Preparation method of 3-chloro-1,2-propanediol |
| CN102786561A (en) * | 2012-08-02 | 2012-11-21 | 中国石油化工股份有限公司 | Method of preparing CAPG for drilling fluid |
-
2017
- 2017-06-27 CN CN201710502448.7A patent/CN107176903B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1233377B (en) * | 1965-02-13 | 1967-02-02 | Raschig Gmbh Dr F | Method for purifying 3-chloro-propanediol- (1, 2) |
| CN101161632A (en) * | 2006-10-10 | 2008-04-16 | 中科院嘉兴中心应用化学分中心 | Preparation method of polyhydric alcohol amine |
| CN101759577A (en) * | 2008-12-25 | 2010-06-30 | 浙江医药股份有限公司新昌制药厂 | Synthesis method of (R)-moprolol |
| CN101928202A (en) * | 2010-01-16 | 2010-12-29 | 张中法 | Production method of high-purity 3-chloro-1, 2-propanediol |
| CN102229523A (en) * | 2011-05-25 | 2011-11-02 | 张中法 | Preparation method of 3-chloro-1,2-propanediol |
| CN102786561A (en) * | 2012-08-02 | 2012-11-21 | 中国石油化工股份有限公司 | Method of preparing CAPG for drilling fluid |
Non-Patent Citations (1)
| Title |
|---|
| "页岩抑制剂阳离子烷基糖苷的合成-环氧氯丙烷水解条件";司西强等;《精细石油化工进展》;20121031;第13卷(第10期);第1-3页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107176903A (en) | 2017-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6771247B2 (en) | Method for producing maleic acid ester by catalytically selective oxidation of lignin | |
| CN103288657A (en) | Modified alcohol amine and preparation method thereof | |
| CN106699511B (en) | Method for recycling organic/inorganic matters in glycerol chlorination distillate | |
| CN103467372A (en) | Combined production method for antioxidant RD and antioxidant FR | |
| CN107325054A (en) | The method of accessory substance recycled in metronidazole production process | |
| CN107176903B (en) | Method for synthesizing 3-chloro-1, 2-propanediol | |
| CN107082740B (en) | Method for improving yield of prenol prepared by chlorination process | |
| CN101708474A (en) | Ionic liquid catalyst, preparation method and application thereof | |
| CN112159362B (en) | Method for purifying intermediate 4,4-dimethylisoxazole-3-one | |
| CN106631689A (en) | Preparation method for sec-butyl alcohol | |
| CN106631783A (en) | Preparation method for n-butyl acetate | |
| CN107759746A (en) | The synthetic method of collapse protective poly-carboxylic acid high-performance water reducing agent | |
| CN102336534B (en) | Preparation process of water reducing agent | |
| CN109265336B (en) | Method for synthesizing gamma-chlorobutyric acid | |
| CN106518671A (en) | Preparation method of butylparaben | |
| CN104710285A (en) | Method for recycling ethylene glycol monomethyl ether | |
| CN110451684A (en) | The processing method of Lauryl Alcohol ester production technology waste water | |
| CN104163753B (en) | A kind of modification L-type molecular sieve catalytic glycerin chlorination is prepared the method for dichlorohydrin | |
| CN110734373B (en) | Method for preparing perfluoro isobutyryl fluoride by reaction kettle liquid phase method | |
| CN109096048A (en) | A kind of method of hydration method synthesizing dihydromyrcenol | |
| WO2018227779A1 (en) | Production process for difluoroethanol | |
| CN104086408A (en) | Preparation method of hydroxyacetic acid | |
| CN104803858B (en) | A method of preparing 4-butyl ammonium fluoride trihydrate | |
| CN107311843A (en) | A kind of 2,3 environmentally friendly dibromo Isosorbide-5-Nitrae butylene glycol preparation methods | |
| CN114805248B (en) | Comprehensive utilization method of industrial low-concentration acetic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |