CN114874078B - 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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- CN114874078B CN114874078B CN202210324259.6A CN202210324259A CN114874078B CN 114874078 B CN114874078 B CN 114874078B CN 202210324259 A CN202210324259 A CN 202210324259A CN 114874078 B CN114874078 B CN 114874078B
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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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- 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 method for synthesizing propylene glycol phenyl ether with high isomer content, which comprises the steps of taking phenol as an initiator and LiOH as a catalyst, adding propylene oxide under the condition of no oxygen to carry out ring-opening etherification reaction, and obtaining the propylene glycol phenyl ether with the isomer content of 2-phenoxy-1-propanol not less than 18%.
Description
Technical Field
The invention relates to the field of organic synthesis reaction, in particular to a synthesis method of propylene glycol phenyl ether with high isomer content.
Background
Propylene glycol phenyl ether is an ideal environment-friendly film forming auxiliary agent. Because of the characteristics of strong dissolving capability, high boiling point, low volatilization, low film forming temperature, good compactness and the like for a plurality of resins, the modified polyurethane resin can be widely applied to oil-soluble or water-soluble paint such as automobile and automobile repair paint, electrophoretic paint, industrial baking paint and ship paint, wood paint, building paint and the like after being compounded.
The production method of the industrial high-grade propylene glycol phenyl ether comprises the following steps: the phenol is subjected to ring opening propylene oxide under the catalysis of KOH or NaOH to prepare a propylene glycol phenyl ether crude product; and then removing phenol and dipropylene glycol phenyl ether in the crude product of the propylene glycol phenyl ether by vacuum rectification, thereby obtaining a propylene glycol phenyl ether product with low phenol content and high purity.
The propylene glycol phenyl ether product mainly comprises two structures: 1-phenoxy-2-propanol and 2-phenoxy-1-propanol. The reaction rate of phenol ring-opening propylene oxide to generate 1-phenoxy-2-propanol is far greater than the reaction rate of phenol ring-opening propylene oxide to generate 2-phenoxy-1-propanol (k 1 & gt k 2), namely the content of 1-phenoxy-2-propanol in propylene glycol phenyl ether products is far higher than that of 2-phenoxy-1-propanol. The proportion of 1-phenoxy-2-propanol in the propylene glycol phenyl ether which is the superior product on the market at present is about 86-88%, and the proportion of the isomer 2-phenoxy-1-propanol is 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 below 5 ℃, so that when a downstream application manufacturer uses in winter, the propylene glycol phenyl ether product can be used after being heated and dissolved in a drying room, the operation of a using unit is difficult, and the energy waste is caused.
The reaction mechanism of preparing propylene glycol phenyl ether by ring-opening propylene oxide under the catalysis condition of phenol is as follows:
it is known that increasing the isomer content of the product makes it difficult to form a stable unit cell structure when the product solidifies, thereby lowering the freezing point of the system. However, no report is made at home and abroad on the literature and patent for increasing the content of isomers to reduce the freezing point of propylene glycol phenyl ether products.
Disclosure of Invention
In view of the foregoing, it is desirable to provide a method for synthesizing propylene glycol phenyl ether having a high isomer content, which solves the problems of the prior art. The technical scheme of the invention is as follows:
a method for synthesizing propylene glycol phenyl ether with high isomer content uses phenol as an initiator and LiOH as a catalyst, and propylene oxide is added under the condition of no oxygen to carry out ring-opening etherification reaction, so that propylene glycol phenyl ether with isomer 2-phenoxy-1-propanol content not lower than 18% is obtained.
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 then introducing propylene oxide to carry out ring-opening etherification reaction;
(3) And (5) degassing after the reaction is finished to obtain the catalyst.
Further, 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 usage amount of the catalyst LiOH is 0.03-0.3% of the sum of the mass of the phenol and the mass of 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 1.0Mpa; 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 1.0Mpa; the reaction temperature is 180-190 ℃; the reaction time is 6 to 9 hours.
Under the reaction temperature condition of 160-200 ℃, the reaction mechanism for preparing the propylene glycol phenyl ether with high isomer ratio by taking LiOH as a catalyst is explained as follows:
the process selects LiOH as a catalyst, and compared with the traditional KOH/NaOH catalyst, the catalyst has weak alkalinity and Li + Is much smaller than Na + /k + The steric hindrance is small when catalyzing the ring-opening propylene oxide. So that the relative reaction rate of 1-phenoxy-2-propanol is higher than that of KOH/NaOH when LiOH is used as catalyst (k) 2 '/k 1 '＞k 2 /k 1 ) The proportion of 2-phenoxy-1-propanol in the product is higher. Compared with KOH/NaOH catalyst, the isomer 2-phenoxy-1-propanol in the propylene glycol phenyl ether prepared by using LiOH as catalyst has higher ratio.
The following reaction equation is the reaction mechanism for preparing propylene glycol phenyl ether by different catalysts:
wherein k is 1 Represents the reaction rate of producing 1-phenoxy-2-propanol with KOH/NaOH as catalyst;
k 2 represents the reaction rate of producing 2-phenoxy-1-propanol with KOH/NaOH as catalyst;
k 1 ' represents the reaction rate of 1-phenoxy-2-propanol over LiOH as catalyst;
k 2 ' indicates the reaction rate of 2-phenoxy-1-propanol with LiOH as catalyst.
k 2 ′/k 1 ′＞k 2 /k 1
The activation energy of the reaction to form 2-phenoxy-1-propanol is greater than the activation energy of the reaction to form 2-phenoxy-1-propanol due to the steric hindrance of the methyl group on propylene oxide. According to the Arrhenius formula, the reaction rate rises faster by increasing the temperature and the reaction activation energy is high. The process selects a reaction temperature range of 160-200 ℃, and compared with the traditional propylene oxide ring opening temperature of 120-140 ℃, the process has faster relative rate (k) of generating 2-phenoxy-1-propanol under the condition of using the same catalyst 2 ”'/k 1 ”'＞k 2 ”/k 1 ") the isomer 2-phenoxy-1-propanol in the product was higher.
The following reaction equation is the reaction mechanism for the propylene glycol phenyl ether at different reaction temperatures:
wherein k is 1 "means the reaction rate at which 1-phenoxy-2-propanol is produced at a reaction temperature of 120 to 140 ℃;
k 2 "means the reaction at 120-140 DEG CReaction rate at which 2-phenoxy-1-propanol is produced at a reaction temperature;
k 1 "' indicates the reaction rate of 1-phenoxy-2-propanol at a reaction temperature of 160 to 200 ℃;
k 2 "' indicates the reaction rate of 2-phenoxy-1-propanol at a reaction temperature of 160 to 200 ℃;
k 2 ″′/k 1 ″′＞k 2 ″/k 1 ″
compared with the prior art, the LiOH is used as a 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 foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
The present invention will be described in detail with reference to examples.
Example 1
244.7kg of phenol and 0.59kg of LiOH were charged into a 500L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 6 hours after the reaction kettle temperature is increased to about 170 ℃ and 151.2kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 1.86 percent of phenol, 95.80 percent of propylene glycol phenyl ether and 2.34 percent of dipropylene glycol phenyl ether. 1 Detection of isomer 2-benzene in product by H-NMRThe ratio of the oxy-1-propanol in the propylene glycol phenyl ether is 18.4 percent.
Example 2
244.7kg of phenol and 0.24kg of LiOH were charged into a 500L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 4 hours after the reaction kettle temperature is raised to about 190 ℃ and 136.1kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 7.81 percent of phenol, 90.32 percent of propylene glycol phenyl ether and 1.87 percent of dipropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 19.7% of the propylene glycol phenyl ether.
Example 3
244.7kg of phenol and 0.35kg of LiOH were charged into a 500L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 6 hours after the reaction kettle temperature is increased to about 180 ℃ and 121.0kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 14.56 percent of phenol, 83.92 percent of propylene glycol phenyl ether and 1.52 percent of dipropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 19.1% of the propylene glycol phenyl ether.
Example 4
244.7kg of phenol and 1.19kg of LiOH were charged into a 500L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 2 hours after the temperature of the reaction kettle is raised to about 160 ℃ and 136.1kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 7.57 percent of phenol, 90.97 percent of propylene glycol phenyl ether and 1.46 percent of dipropylene glycol phenyl ether. 1 H-NMR detected that the content of the homomeric isomer 2-phenoxy-1-propanol in the propylene glycol phenyl ether was 18.3%.
Example 5
At 50244.7kg of phenol and 0.12kg of LiOH were added to a 0L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 1 hour after the reaction kettle temperature is increased to about 200 ℃ and 166.1kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 0.01 percent of phenol, 88.64 percent of propylene glycol phenyl ether, 10.3 percent of dipropylene glycol phenyl ether and 1.05 percent of tripropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 18.6% of the propylene glycol phenyl ether.
Comparative example 1
244.7kg of phenol and 0.24kg of KOH were charged into a 500L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 4 hours after the reaction kettle temperature is raised to about 190 ℃ and 136.1kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 8.14 percent of phenol, 89.58 percent of propylene glycol phenyl ether and 2.28 percent of dipropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 15.2% of the propylene glycol phenyl ether.
Comparative example 2
244.7kg of phenol and 0.35kg of LiOH were charged into a 500L pressure-resistant reaction vessel, and a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 6 hours after the reaction kettle temperature is increased to about 120 ℃ and 121.0kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 13.72 percent of phenol, 85.34 percent of propylene glycol phenyl ether and 0.94 percent of dipropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 16.2% of the 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 a propylene oxide metering tank was connected to the pressure vessel. At the position ofThe reaction pressure is less than or equal to 1.0Mpa, air is replaced by nitrogen for 3 times at the temperature of 60 ℃, then vacuum is pumped, 136.1kg of propylene oxide is introduced when the temperature of the reaction kettle is raised to about 160 ℃, and the reaction is continued for 2 hours after 3 hours are completed. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 7.87 percent of phenol, 90.17 percent of propylene glycol phenyl ether and 1.96 percent of dipropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 15.6% of the 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 a propylene oxide metering tank was connected to the pressure vessel. And (3) at the reaction pressure of less than or equal to 1.0Mpa and the temperature of 60 ℃, replacing air with nitrogen for 3 times, vacuumizing, and continuing to react for 2 hours after the temperature of the reaction kettle is raised to about 120 ℃ and 136.1kg of propylene oxide is introduced. And after the reaction is finished, degassing, sampling and detecting. The GC detection product contains about 7.13 percent of phenol, 91.75 percent of propylene glycol phenyl ether and 1.12 percent of dipropylene glycol phenyl ether. 1 H-NMR detects that the isomer 2-phenoxy-1-propanol accounts for 13.5% of the propylene glycol phenyl ether.
In example 2, the molar ratio of phenol to propylene oxide was 1:0.9, with the highest proportion of isomer 2-phenoxy-1-propanol in the product. As can be seen from examples 1 to 5, the content of the isomer 2-phenoxy-1-propanol in the synthesized propylene glycol phenyl ether is more than or equal to 18.0% by taking LiOH as a catalyst and the reaction temperature is between 160 and 200 ℃. Comparing comparative example 1 with example 2, comparative example 3 and example 4 show that the isomer 2-phenoxy-1-propanol in propylene glycol phenyl ether prepared with LiOH as catalyst has a higher ratio than the KOH/NaOH catalyst. As is clear from comparison of comparative example 3 and comparative example 4, the higher the reaction temperature, the faster the reaction rate rises, and the higher the proportion of the isomer 2-phenoxy-1-propanol in the product.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. A method for synthesizing propylene glycol phenyl ether with high isomer content is characterized in that: phenol is used as an initiator, liOH is used as a catalyst, propylene oxide is added under the condition of no oxygen, and ring-opening etherification reaction is carried out at the reaction temperature of 160-200 ℃ to obtain propylene glycol phenyl ether with the isomer 2-phenoxy-1-propanol content of not less than 18%.
2. The method for synthesizing the propylene glycol phenyl ether with high isomer content according to claim 1, which is characterized in that: 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 then introducing propylene oxide to carry out ring-opening etherification reaction;
(3) And (5) degassing after the reaction is finished to obtain the catalyst.
3. The method for synthesizing the propylene glycol phenyl ether with high isomer content according to claim 2, which is characterized in that: the molar ratio of the phenol to the propylene oxide is 1 (0.8-1.1).
4. A method for synthesizing high isomer content propylene glycol phenyl ether according to claim 3, wherein: the molar ratio of the phenol to the propylene oxide is 1:0.9.
5. The method for synthesizing the propylene glycol phenyl ether with high isomer content according to claim 2, which is characterized in that: 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 the propylene glycol phenyl ether with high isomer content according to claim 2, which is characterized in that: the conditions of the ring-opening etherification reaction are controlled as follows: the reaction pressure is less than or equal to 1.0Mpa; the reaction time is 2-10 hours.
7. The method for synthesizing the propylene glycol phenyl ether with high isomer content according to claim 6, which is characterized in that: the conditions of the ring-opening etherification reaction are controlled as follows: the reaction pressure is less than or equal to 1.0Mpa; the reaction temperature is 180-190 ℃; the reaction time is 6 to 9 hours.
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| WO2018160879A2 (en) * | 2017-03-01 | 2018-09-07 | Polnox Corporation | Macromolecular corrosion (mcin) inhibitors: structures, methods of making and using the same |
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| 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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