CN114874078A - Synthesis method of propylene glycol phenyl ether with high isomer content - Google Patents
Synthesis method of propylene glycol phenyl ether with high isomer content Download PDFInfo
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- CN114874078A CN114874078A CN202210324259.6A CN202210324259A CN114874078A CN 114874078 A CN114874078 A CN 114874078A CN 202210324259 A CN202210324259 A CN 202210324259A CN 114874078 A CN114874078 A CN 114874078A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a synthesis method of high isomer content propylene glycol phenyl ether, which takes phenol as an initiator and LiOH as a catalyst, and adds propylene oxide to carry out ring opening etherification reaction under the condition of no oxygen, so as to obtain the propylene glycol phenyl ether with isomer 2-phenoxy-1-propanol content not less than 18%.
Description
Technical Field
The invention relates to the field of organic synthesis reaction, in particular to a synthesis method of high-isomer-content propylene glycol phenyl ether.
Background
Propylene glycol phenyl ether is an ideal environment-friendly film-forming aid. Because of the characteristics of strong dissolving capacity, high boiling point, low volatilization, low film forming temperature, good compactness and the like, the modified epoxy resin is widely applied to oil-soluble or water-soluble coatings such as automobile and automobile repairing coatings, electrophoretic coatings, industrial baking paints, ship paints, wood paints, building coatings and the like.
The production method of the industrial superior propylene glycol phenyl ether comprises the following steps: opening ring of epoxypropane by phenol under the catalysis of KOH or NaOH to prepare a crude product of propylene glycol phenyl ether; and then the phenol and the dipropylene glycol phenyl ether in the crude product of the propylene glycol phenyl ether are removed through rectification under reduced pressure, so that the propylene glycol phenyl ether product with low phenol content and high purity is obtained.
The propylene glycol phenyl ether product mainly contains two structures: 1-phenoxy-2-propanol and 2-phenoxy-1-propanol. Due to steric hindrance of methyl on propylene oxide, the reaction rate of the phenol ring opening propylene oxide to generate 1-phenoxy-2-propanol is far higher than the reaction rate of the phenol ring opening propylene oxide to generate 2-phenoxy-1-propanol (k1 > k2), i.e. the content of 1-phenoxy-2-propanol in the propylene glycol phenyl ether product is far higher than that of 2-phenoxy-1-propanol. The 1-phenoxy-2-propanol in the current market superior product propylene glycol phenyl ether accounts for about 86-88%, and the isomer 2-phenoxy-1-propanol accounts for about 12-14%. Wherein the freezing point of the 1-phenoxy-2-propanol is about 11 ℃. Therefore, the propylene glycol phenyl ether product on the market is easy to solidify in the environment of lower than 5 ℃, so that a downstream application manufacturer can use the propylene glycol phenyl ether product after being heated and dissolved in a drying room in winter, thereby bringing difficulty to operation of a user and causing energy waste.
The reaction mechanism of the phenol for preparing the propylene glycol phenyl ether by opening the epoxy propane under the catalytic condition is as follows:
it is known that increasing the isomer content of a product makes it difficult to form a stable unit cell structure when the product is solidified, thereby lowering the freezing point of the system. However, at present, no report is found in the literature and patents on lowering the freezing point of propylene glycol phenyl ether products by increasing the content of isomers at home and abroad.
Disclosure of Invention
In view of the above, there is a need to provide a method for synthesizing propylene glycol phenyl ether with high isomer content, which solves the problems of the prior art. The technical scheme of the invention is as follows:
a synthesis method of high isomer content propylene glycol phenyl ether is characterized by using phenol as an initiator and LiOH as a catalyst, and adding epoxypropane to perform ring-opening etherification reaction under the condition of no oxygen to obtain the propylene glycol phenyl ether with the isomer content of 2-phenoxy-1-propanol not less than 18%.
Further, the synthesis method comprises the following steps:
(1) adding phenol and LiOH into a pressure-resistant reaction kettle, uniformly mixing, replacing air with nitrogen for 3 times at 60 ℃, and vacuumizing;
(2) raising the temperature of the pressure-resistant reaction kettle to a certain temperature, and introducing epoxypropane to carry out ring-opening etherification reaction;
(3) degassing after the reaction is finished to obtain the catalyst.
Furthermore, the molar ratio of the phenol to the propylene oxide is 1 (0.8-1.1).
Preferably, the molar ratio of phenol to propylene oxide is 1: 0.9.
further, the use amount of the LiOH catalyst is 0.03-0.3% of the mass sum of the phenol and the propylene oxide.
Further, the conditions of the ring-opening etherification reaction are controlled as follows: the reaction pressure is less than or equal to 1.0 Mpa; the reaction temperature is 160-200 ℃; the reaction time is 2-10 hours.
Preferably, the conditions of the ring-opening etherification reaction are controlled as follows: the reaction pressure is less than or equal to 1.0 Mpa; the reaction temperature is 180-190 ℃; the reaction time is 6-9 hours.
The reaction mechanism of preparing the propylene glycol phenyl ether with high isomer ratio by using LiOH as a catalyst at the reaction temperature of 160-200 ℃ is explained as follows:
the process selects LiOH as catalystThe catalyst is less basic than conventional KOH/NaOH catalysts and Li + Much less than Na in volume + /k + And when the ring opening of the propylene oxide is catalyzed, the steric hindrance is small. So that when LiOH is used as a catalyst, the relative reaction rate of 1-phenoxy-2-propanol is higher than that of KOH/NaOH (k) 2 '/k 1 '＞k 2 /k 1 ) The proportion of 2-phenoxy-1-propanol in the product is higher. Compared with a KOH/NaOH catalyst, the ratio of the isomer 2-phenoxy-1-propanol in the propylene glycol phenyl ether prepared by using LiOH as the catalyst is higher.
The following reaction equation is the reaction mechanism for the preparation of propylene glycol phenyl ether for different catalysts:
wherein k is 1 The reaction rate of generating 1-phenoxy-2-propanol by using KOH/NaOH as a catalyst is shown;
k 2 the reaction rate of generating 2-phenoxy-1-propanol by using KOH/NaOH as a catalyst is shown;
k 1 ' represents a reaction rate of producing 1-phenoxy-2-propanol using LiOH as a catalyst;
k 2 ' represents the reaction rate of 2-phenoxy-1-propanol with LiOH as a catalyst.
k 2 ′/k 1 ′＞k 2 /k 1
The activation energy of the reaction to produce 2-phenoxy-1-propanol is greater than the activation energy to produce 2-phenoxy-1-propanol due to steric effects of the methyl group on the propylene oxide. According to the Arrhenius formula, the reaction rate is increased more rapidly by increasing the temperature and the reaction activation energy. The process selects a reaction temperature range of 160-200 ℃, and compared with the traditional propylene oxide ring-opening temperature of 120-140 ℃, the relative speed (k) of the process for generating the 2-phenoxy-1-propanol is higher under the condition of using the same catalyst 2 ”'/k 1 ”'＞k 2 ”/k 1 "), the proportion of isomer 2-phenoxy-1-propanol in the product is higher.
The following reaction equation gives the reaction mechanism for propylene glycol phenyl ether for different reaction temperatures:
wherein k is 1 "represents the reaction rate of producing 1-phenoxy-2-propanol at a reaction temperature of 120 to 140 ℃;
k 2 "represents the reaction rate of generating 2-phenoxy-1-propanol at the reaction temperature of 120-140 ℃;
k 1 "' represents the reaction rate of generating 1-phenoxy-2-propanol at the reaction temperature of 160-200 ℃;
k 2 "' represents the reaction rate of generating 2-phenoxy-1-propanol at the reaction temperature of 160-200 ℃;
k 2 ″′/k 1 ″′＞k 2 ″/k 1 ″
compared with the prior art, the LiOH selected by the invention is used as the catalyst, the alkalinity is weak, the catalytic steric hindrance is small, and the reaction temperature is high, so that the content of the isomer 2-phenoxy-1-propanol in the synthesized propylene glycol phenyl ether is more than or equal to 18.0%.
Detailed Description
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The present invention will be described in detail with reference to examples.
Example 1
A500L pressure resistant reactor was charged with 244.7kg of phenol and 0.59kg of LiOH, and an propylene oxide metering tank was connected to the pressure reactor. Replacing air with nitrogen gas at 60 deg.C under reaction pressure of 1.0Mpa or less for 3 times, and vacuumizingAfter the temperature of the reaction kettle rises to about 170 ℃, 151.2kg of propylene oxide starts to be introduced, and the reaction is continued for 6 hours after the introduction of the propylene oxide is finished for 4 hours. And degassing after the reaction is finished, and sampling and detecting. The product was checked by GC for phenol content of about 1.86%, propylene glycol phenyl ether content of 95.80%, and dipropylene glycol phenyl ether content of 2.34%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 18.4% in propylene glycol phenyl ether.
Example 2
A500L pressure resistant reactor was charged with 244.7kg of phenol and 0.24kg of LiOH, and an propylene oxide metering tank was connected to the pressure reactor. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 136.1kg of propylene oxide when the temperature of the reaction kettle rises to about 190 ℃, and continuing to react for 4 hours after 2 hours of introduction. And degassing after the reaction is finished, and sampling and detecting. The product was checked by GC for phenol content of about 7.81%, propylene glycol phenyl ether content of 90.32%, and dipropylene glycol phenyl ether content of 1.87%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 19.7% in propylene glycol phenyl ether.
Example 3
A500L pressure resistant reactor was charged with 244.7kg of phenol and 0.35kg of LiOH, and an propylene oxide metering tank was connected to the pressure reactor. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 121.0kg of propylene oxide when the temperature of the reaction kettle rises to about 180 ℃, and continuing to react for 6 hours after the introduction of the propylene oxide is finished for 3 hours. And degassing after the reaction is finished, and sampling and detecting. The product was checked by GC for phenol content about 14.56%, propylene glycol phenyl ether content 83.92%, and dipropylene glycol phenyl ether content 1.52%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 19.1% in propylene glycol phenyl ether.
Example 4
A500L pressure resistant reactor was charged with 244.7kg of phenol and 1.19kg of LiOH, and an propylene oxide metering tank was connected to the pressure reactor. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 136.1kg of propylene oxide when the temperature of the reaction kettle rises to about 160 ℃, and continuing to react for 2 hours after the introduction of the propylene oxide is finished for 3 hours. Degassing after the reactionAnd sampling and detecting. The product was checked by GC for phenol content of about 7.57%, propylene glycol phenyl ether content of 90.97%, and dipropylene glycol phenyl ether content of 1.46%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 18.3% in propylene glycol phenyl ether.
Example 5
244.7kg of phenol and 0.12kg of LiOH were charged into a 500L pressure-resistant reaction vessel, and an propylene oxide metering tank was connected to the pressure vessel. At the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air by nitrogen for 3 times, vacuumizing, starting to introduce 166.1kg of propylene oxide when the temperature of the reaction kettle rises to about 200 ℃, and continuing to react for 1 hour after the introduction is finished for 1 hour. And degassing after the reaction is finished, and sampling and detecting. The GC detection of the product showed about 0.01% phenol, 88.64% propylene glycol phenyl ether, 10.3% dipropylene glycol phenyl ether and 1.05% tripropylene glycol phenyl ether. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 18.6% in propylene glycol phenyl ether.
Comparative example 1
A500L pressure resistant reactor was charged with 244.7kg of phenol and 0.24kg of KOH, and a propylene oxide metering tank was connected to the pressure reactor. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 136.1kg of propylene oxide when the temperature of the reaction kettle rises to about 190 ℃, and continuing to react for 4 hours after 2 hours of introduction. And degassing after the reaction is finished, and sampling and detecting. The product was checked by GC for phenol content about 8.14%, propylene glycol phenyl ether content 89.58%, and dipropylene glycol phenyl ether content 2.28%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 15.2% in propylene glycol phenyl ether.
Comparative example 2
A500L pressure resistant reactor was charged with 244.7kg of phenol and 0.35kg of LiOH, and an propylene oxide metering tank was connected to the pressure reactor. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 121.0kg of propylene oxide when the temperature of the reaction kettle rises to about 120 ℃, and continuing to react for 6 hours after the introduction of the propylene oxide is finished for 3 hours. And degassing after the reaction is finished, and sampling and detecting. GC detects the phenol content in the product to be about 13.72 percent, the propylene glycol phenyl ether content to be 85.34 percent, and the dipropylene glycol benzeneThe ether content was 0.94%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 16.2% in propylene glycol phenyl ether.
Comparative example 3
244.7kg of phenol and 1.19kg of NaOH were charged into a 500L pressure-resistant reaction vessel, and an propylene oxide metering tank was connected to the pressure vessel. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 136.1kg of propylene oxide when the temperature of the reaction kettle rises to about 160 ℃, and continuing to react for 2 hours after 3 hours of introduction. And degassing after the reaction is finished, and sampling and detecting. The product was checked by GC for phenol content of about 7.87%, propylene glycol phenyl ether content of 90.17%, and dipropylene glycol phenyl ether content of 1.96%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 15.6% in propylene glycol phenyl ether.
Comparative example 4
244.7kg of phenol and 1.19kg of NaOH were charged into a 500L pressure-resistant reaction vessel, and an propylene oxide metering tank was connected to the pressure vessel. Replacing air with nitrogen for 3 times under the reaction pressure of less than or equal to 1.0Mpa and at the temperature of 60 ℃, vacuumizing, starting to introduce 136.1kg of propylene oxide when the temperature of the reaction kettle rises to about 120 ℃, and continuing to react for 2 hours after the introduction of the propylene oxide is finished for 3 hours. And degassing after the reaction is finished, and sampling and detecting. The product was checked by GC for phenol content of about 7.13%, propylene glycol phenyl ether content of 91.75%, and dipropylene glycol phenyl ether content of 1.12%. 1 H-NMR showed that the isomer 2-phenoxy-1-propanol in the product was 13.5% in propylene glycol phenyl ether.
In example 2, the molar ratio of phenol to propylene oxide was 1:0.9, and the product had the highest ratio of isomer 2-phenoxy-1-propanol. From the examples 1 to 5, it can be seen that the ratio of 2-phenoxy-1-propanol, which is an isomer in the synthesized propylene glycol phenyl ether, is more than or equal to 18.0% by using LiOH as a catalyst and the reaction temperature is 160-200 ℃. Comparing comparative example 1 and example 2, and comparative example 3 and example 4, it can be seen that the isomer 2-phenoxy-1-propanol is higher in propylene glycol phenyl ether prepared using LiOH as a catalyst, relative to KOH/NaOH catalyst. Comparing comparative example 3 and comparative example 4, it can be seen that the higher the reaction temperature, the faster the reaction rate rises, and the higher the proportion of isomer 2-phenoxy-1-propanol in the product.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. A method for synthesizing propylene glycol phenyl ether with high isomer content is characterized in that: taking phenol as an initiator and LiOH as a catalyst, and adding propylene oxide to perform ring-opening etherification reaction under the condition of no oxygen to obtain propylene glycol phenyl ether with the isomer 2-phenoxy-1-propanol content of not less than 18%.
2. The method for synthesizing propylene glycol phenyl ether with high isomer content according to claim 1, wherein the method comprises the following steps: the synthesis method comprises the following steps:
(1) adding phenol and LiOH into a pressure-resistant reaction kettle, uniformly mixing, replacing air with nitrogen for 3 times at 60 ℃, and vacuumizing;
(2) raising the temperature of the pressure-resistant reaction kettle to a certain temperature, and introducing epoxypropane to carry out ring-opening etherification reaction;
(3) degassing after the reaction is finished to obtain the catalyst.
3. The method for synthesizing propylene glycol phenyl ether with high isomer content according to claim 2, wherein the method comprises the following steps: the molar ratio of the phenol to the propylene oxide is 1 (0.8-1.1).
4. The method for synthesizing propylene glycol phenyl ether with high isomer content according to claim 3, wherein the method comprises the following steps: the molar ratio of phenol to propylene oxide was 1: 0.9.
5. The method for synthesizing propylene glycol phenyl ether with high isomer content according to claim 2, wherein the method comprises the following steps: the dosage of the catalyst is 0.03-0.3% of the sum of the mass of the phenol and the mass of the propylene oxide.
6. The method for synthesizing propylene glycol phenyl ether with high isomer content according to claim 2, wherein the method comprises the following steps: the conditions of the ring-opening etherification reaction are controlled as follows: the reaction pressure is less than or equal to 1.0 Mpa; the reaction temperature is 160-200 ℃; the reaction time is 2-10 hours.
7. The method for synthesizing propylene glycol phenyl ether with high isomer content according to claim 6, wherein the method comprises the following steps: the conditions of the ring-opening etherification reaction are controlled as follows: the reaction pressure is less than or equal to 1.0 Mpa; the reaction temperature is 180-190 ℃; the reaction time is 6-9 hours.
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Citations (4)
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| CN101712600A (en) * | 2008-10-07 | 2010-05-26 | 抚顺佳化聚氨酯有限公司 | Method for preparing ethylene glycol phenyl ether, propylene glycol phenyl ether and butylene glycol phenyl ether |
| CN102887830A (en) * | 2012-09-04 | 2013-01-23 | 苏州弘森药业有限公司 | Preparation method of phenoxybenzamine hydrochloride |
| CN106478385A (en) * | 2015-09-02 | 2017-03-08 | 奇里茨应用技术（上海）有限公司 | A kind of prepare high-purity propylene glycol phenylate of Determination of Trace Phenol or the method for ethylene glycol phenyl ether |
| US20210130722A1 (en) * | 2017-03-01 | 2021-05-06 | Polnox Corporation | Macromolecular corrosion (mcin) inhibitors: structures, methods of making and using the same |
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| CN101712600A (en) * | 2008-10-07 | 2010-05-26 | 抚顺佳化聚氨酯有限公司 | Method for preparing ethylene glycol phenyl ether, propylene glycol phenyl ether and butylene glycol phenyl ether |
| CN102887830A (en) * | 2012-09-04 | 2013-01-23 | 苏州弘森药业有限公司 | Preparation method of phenoxybenzamine hydrochloride |
| CN106478385A (en) * | 2015-09-02 | 2017-03-08 | 奇里茨应用技术（上海）有限公司 | A kind of prepare high-purity propylene glycol phenylate of Determination of Trace Phenol or the method for ethylene glycol phenyl ether |
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