CN108409567A - A kind of continuous producing method of hydroxy propyl methacrylate - Google Patents
A kind of continuous producing method of hydroxy propyl methacrylate Download PDFInfo
- Publication number
- CN108409567A CN108409567A CN201810058899.0A CN201810058899A CN108409567A CN 108409567 A CN108409567 A CN 108409567A CN 201810058899 A CN201810058899 A CN 201810058899A CN 108409567 A CN108409567 A CN 108409567A
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- CN
- China
- Prior art keywords
- propyl methacrylate
- hydroxy propyl
- distillation
- methacrylic acid
- producing method
- 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.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of continuous producing methods of hydroxy propyl methacrylate, include the following steps：Make methacrylic acid, catalyst and polymerization inhibitor are through entering tank reactor, it is passed through propylene oxide and at 60~80 DEG C, ring-opening reaction is carried out under 0.25~0.1MPa, reaction mixture is made, condensation separation obtains excess propylene oxide and crude methacrylic acid hydroxypropyl acrylate, crude methacrylic acid hydroxypropyl acrylate is set to enter intermediate maturity storage tank and polymerization inhibitor progress short distance rectifying, discharging is hydroxy propyl methacrylate and a raffinate, raffinate is subjected to short distance rectifying again, discharging is hydroxy propyl methacrylate and secondary raffinate, product of distillation is obtained after secondary raffinate is distilled, product of distillation is recycled and carries out short-path distillation and distillation, realize the continuous production of hydroxy propyl methacrylate.The advantage of the invention is that：Reaction temperature is low, and side reaction is reduced, and is reduced the loss of raw material, is improved the conversion ratio of raw material, to improve product quality.
Description
Technical field
The present invention relates to field of chemical technology, are more particularly to a kind of continuous production side of hydroxy propyl methacrylate
Method.
Background technology
Hydroxy propyl methacrylate is a kind of important industrial chemicals, due to the only of carbochain double bond, hydroxyl and ester group
Special structure, can be through homopolymerization and copolymerization multiple polymers as polymerized monomer, and such polymer bonding is not secured, easy-peel
It falls, is flexible and flexible at room temperature, while there is good water resistance, therefore being widely used in synthesizing methyl acrylic acid tree
Fat, light-cured resin, optical resin, coating etc..
Industrial production hydroxy propyl methacrylate mainly has 2 kinds of techniques at present, the first is added in methacrylic acid
Enter ferric rhodanate, tetramethyl ammonium chloride etc. and a little hydroquinone, be heated with stirring to 90 DEG C, under nitrogen protection, is passed through epoxy
Propane gas reacts about 2h, and reaction product is cooled to 60 DEG C, is evaporated under reduced pressure after adding a small amount of hydroquinone, collects 86-89 DEG C
(0.67kPa) fraction is got product, and 80% or more yield, such method is disadvantageous in that propylene oxide is inflammable and explosive, right
Production equipment and operating condition require stringent, technical merit requirement height.Second is that metering system acid potassium salt is being hindered with chloropropyl alcohol
Reaction generates crude methacrylic acid -2- hydroxy propyl esters in the presence of poly- agent, through saltouing, being refining to obtain finished product, the synthesis week of such method
Phase is long, unstable product quality, haves the shortcomings that the filtration problem of by-product and chloropropyl alcohol toxicity are big.
Invention content
Technical problem to be solved by the present invention lies in the hydroxyethyl methacrylates for providing a kind of stable quality, mild condition
The continuous producing method of propyl ester.
The present invention is to solve above-mentioned technical problem by the following technical programs：
A kind of continuous producing method of hydroxy propyl methacrylate, includes the following steps：
So that methacrylic acid, propylene oxide, catalyst and polymerization inhibitor is respectively enterd in tank reactor, 60~80 DEG C,
Carry out ring-opening reaction under 0.25~0.1MPa, crude methacrylic acid hydroxypropyl acrylate be made, make the crude methacrylic acid hydroxypropyl acrylate into
Enter intermediate maturity storage tank, and polymerization inhibitor added into the intermediate maturity storage tank, be then sent in short-path distillation kettle carry out it is short
Journey rectifying discharges as hydroxy propyl methacrylate and a raffinate, a raffinate is carried out short distance rectifying again, discharging is
The secondary raffinate is entered after distillation still carries out distillation reaction and obtains distillation production by hydroxy propyl methacrylate and secondary raffinate
The product of distillation is reentered short-path distillation kettle by object, is carried out short-path distillation and distillation to recycle, is realized methacrylic acid
The continuous production of hydroxypropyl acrylate.
Preferably, in the unit interval, the mass ratio that feeds intake of the methacrylic acid and propylene oxide is 5~7:4.
Preferably, the additive amount of the catalyst is 0.1~0.5wt%, and the wt% is with methacrylic acid and epoxy third
The total weight of alkane.
Preferably, the additive amount of polymerization inhibitor is 0.2~0.6wt% in the material-compound tank, is hindered in the intermediate maturity storage tank
The additive amount of poly- agent is 0.1~0.4wt%, and the wt% is with the total weight of methacrylic acid and propylene oxide.
Preferably, the catalyst is iron chloride.
Preferably, the polymerization inhibitor is ZJ-705.
Preferably, the operating temperature of the intermediate maturity storage tank is 20~30 DEG C, operating pressure is normal pressure, and the short distance is steamed
The operating temperature for evaporating kettle is 50~70 DEG C, operating pressure is -0.05~-0.01MPa, the operating temperature of the distillation still is 80~
100 DEG C, operating pressure be -0.05~-0.01MPa.
The present invention has the following advantages compared with prior art：The reaction temperature of the production method of the present invention is low, and side reaction subtracts
It is few, the loss of raw material is reduced, the conversion ratio of raw material is improved, so that product quality has obtained further being promoted；And
And entire production link all carries out in closed environment, is generated without exhaust gas, waste water, by-product, does not have any dirt to environment
Dye；The temperature of entire production link is all at 90 degrees Celsius hereinafter, energy consumption substantially reduces.
Description of the drawings
Fig. 1 is the flow chart of the continuous producing method of the hydroxy propyl methacrylate of the application.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
As shown in Figure 1, methacrylic acid, propylene oxide, catalyst iron chloride and polymerization inhibitor ZJ-705 is made to respectively enter kettle
In formula reactor, ring-opening reaction is carried out at 80 DEG C, 0.25MPa, successive reaction generates hydroxy propyl methacrylate.Control reaction
Device circulating water temperature stablizes temperature of reactor, ensures reaction safety, makes crude methacrylic acid hydroxypropyl acrylate into 25 DEG C, normal pressure state
Intermediate maturity storage tank, and add polymerization inhibitor into intermediate maturity storage tank, be delivered to 70 DEG C, the short-path distillations of -0.01MPa states
Short distance rectifying is carried out in kettle, bottom discharging is hydroxy propyl methacrylate, is directly entered finished pot；Side discharge hole for discharge is primary
Raffinate, a raffinate carry out short distance rectifying again through pumping, and discharge as hydroxy propyl methacrylate and secondary raffinate, by secondary raffinate
Into 100 DEG C, -0.01MPa states distillation still carry out distillation reaction after obtain product of distillation, by the product of distillation again into
Enter short-path distillation kettle, the secondary raffinate after short-path distillation through pump beat to raffinate gravity tank, by gravity tank gravity flow into distillation still into
Row distillation, gained product of distillation carries out short-path distillation again after distillation；Short-path distillation and distillation successively cycle carry out, be made compared with
High-content finished product realizes continuous production.Wherein, the mass ratio that feeds intake of methacrylic acid and propylene oxide is 6:4, catalyst chlorination
The additive amount of iron is the 0.3wt% of the total weight of methacrylic acid and propylene oxide, the addition of polymerization inhibitor ZJ-705 in material-compound tank
Amount is the 0.4wt% of the total weight of methacrylic acid and propylene oxide, the additive amount of polymerization inhibitor ZJ-705 in intermediate maturity storage tank
For the 0.3wt% of the total weight of methacrylic acid and propylene oxide.
Embodiment 2
Hydroxy propyl methacrylate is produced in the method for embodiment 1, is differed only in：It is opened at 60 DEG C, 0.75MPa
Ring reacts, and the mass ratio that feeds intake of methacrylic acid and propylene oxide is 4:6, the additive amount of catalyst iron chloride is methacrylic acid
With the 0.1wt% of the total weight of propylene oxide, the additive amount of polymerization inhibitor ZJ-705 is methacrylic acid and epoxy third in material-compound tank
The 0.2wt% of the total weight of alkane, the additive amount of polymerization inhibitor ZJ-705 is methacrylic acid and propylene oxide in intermediate maturity storage tank
Total weight 0.1wt%.
Embodiment 3
Hydroxy propyl methacrylate is produced in the method for embodiment 1, is differed only in：It is opened at 70 DEG C, 0.1MPa
Ring reacts, and the mass ratio that feeds intake of methacrylic acid and propylene oxide is 4:4, the additive amount of catalyst iron chloride is methacrylic acid
With the 0.5wt% of the total weight of propylene oxide, the additive amount of polymerization inhibitor ZJ-705 is methacrylic acid and epoxy third in material-compound tank
The 0.6wt% of the total weight of alkane, the additive amount of polymerization inhibitor ZJ-705 is methacrylic acid and propylene oxide in intermediate maturity storage tank
Total weight 0.4wt%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (7)
1. a kind of continuous producing method of hydroxy propyl methacrylate, which is characterized in that include the following steps：
So that methacrylic acid, propylene oxide, catalyst and polymerization inhibitor is respectively enterd in tank reactor, 60~80 DEG C, 0.25
Ring-opening reaction is carried out under~0.1MPa, crude methacrylic acid hydroxypropyl acrylate is made, in so that the crude methacrylic acid hydroxypropyl acrylate is entered
Between finished product storage tank, and add polymerization inhibitor into the intermediate maturity storage tank, be then sent in short-path distillation kettle and carry out short distance essence
It evaporates, discharges as hydroxy propyl methacrylate and a raffinate, a raffinate is subjected to short distance rectifying again, is discharged as methyl
The secondary raffinate is entered after distillation still carries out distillation reaction and obtains product of distillation by hydroxypropyl acrylate and secondary raffinate, will
The product of distillation reenters short-path distillation kettle, carries out short-path distillation and distillation to recycle, realizes methacrylic acid hydroxypropyl
The continuous production of ester.
2. the continuous producing method of hydroxy propyl methacrylate according to claim 1, which is characterized in that the unit interval
Interior, the mass ratio that feeds intake of the methacrylic acid and propylene oxide is 5~7:4.
3. the continuous producing method of hydroxy propyl methacrylate according to claim 1, which is characterized in that the catalyst
Additive amount be 0.1~0.5wt%, the wt% is with the total weight of methacrylic acid and propylene oxide.
4. the continuous producing method of hydroxy propyl methacrylate according to claim 1, which is characterized in that the material-compound tank
The additive amount of middle polymerization inhibitor is 0.2~0.6wt%, in the intermediate maturity storage tank additive amount of polymerization inhibitor be 0.1~
0.4wt%, the wt% is with the total weight of methacrylic acid and propylene oxide.
5. the continuous producing method of hydroxy propyl methacrylate according to claim 1, which is characterized in that the catalyst
For iron chloride.
6. the continuous producing method of hydroxy propyl methacrylate according to claim 1, which is characterized in that the polymerization inhibitor
For ZJ-705.
7. the continuous producing method of hydroxy propyl methacrylate according to claim 1, which is characterized in that the centre at
The operating temperature of product storage tank is 20~30 DEG C, operating pressure is normal pressure, the operating temperature of the short-path distillation kettle is 50~70 DEG C,
Operating pressure is -0.05~-0.01MPa, the operating temperature of the distillation still is 80~100 DEG C, operating pressure be -0.05~-
0.01MPa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810058899.0A CN108409567A (en) | 2018-01-22 | 2018-01-22 | A kind of continuous producing method of hydroxy propyl methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810058899.0A CN108409567A (en) | 2018-01-22 | 2018-01-22 | A kind of continuous producing method of hydroxy propyl methacrylate |
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| CN108409567A true CN108409567A (en) | 2018-08-17 |
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| CN201810058899.0A Withdrawn CN108409567A (en) | 2018-01-22 | 2018-01-22 | A kind of continuous producing method of hydroxy propyl methacrylate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634414A (en) * | 2021-10-29 | 2022-06-17 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
| CN114890890A (en) * | 2022-05-09 | 2022-08-12 | 中建安装集团有限公司 | Process for recovering methacrylic acid or/and ester residual liquid thereof by catalytic cracking coupled rectification |
| WO2022243038A1 (en) * | 2021-05-19 | 2022-11-24 | Röhm Gmbh | Process for preparing a polymerization-prone compound |
-
2018
- 2018-01-22 CN CN201810058899.0A patent/CN108409567A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022243038A1 (en) * | 2021-05-19 | 2022-11-24 | Röhm Gmbh | Process for preparing a polymerization-prone compound |
| CN114634414A (en) * | 2021-10-29 | 2022-06-17 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
| CN114634414B (en) * | 2021-10-29 | 2023-01-03 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
| CN114890890A (en) * | 2022-05-09 | 2022-08-12 | 中建安装集团有限公司 | Process for recovering methacrylic acid or/and ester residual liquid thereof by catalytic cracking coupled rectification |
| CN114890890B (en) * | 2022-05-09 | 2024-02-06 | 中建安装集团有限公司 | Process for recovering methacrylic acid and/or ester raffinate thereof by catalytic cracking coupling rectification |
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| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180817 |
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