CN108409566A - It is a kind of（Methyl）The preparation method of hydroxypropyl acrylate - Google Patents
It is a kind of（Methyl）The preparation method of hydroxypropyl acrylate Download PDFInfo
- Publication number
- CN108409566A CN108409566A CN201810058551.1A CN201810058551A CN108409566A CN 108409566 A CN108409566 A CN 108409566A CN 201810058551 A CN201810058551 A CN 201810058551A CN 108409566 A CN108409566 A CN 108409566A
- Authority
- CN
- China
- Prior art keywords
- methyl
- hydroxypropyl acrylate
- preparation
- short
- 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.)
- Pending
Links
Classifications
-
- 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
Landscapes
- 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 preparation methods of (methyl) hydroxypropyl acrylate, include the following steps：Make (methyl) acrylic acid and propylene oxide with 1 at 60~80 DEG C:1~1.5 molar ratio is reacted in a kettle in the presence of catalyst and polymerization inhibitor, crude product (methyl) hydroxypropyl acrylate is made, crude product (methyl) hydroxypropyl acrylate is sent into short-path distillation kettle and carries out short distance rectifying, finished product (methyl) hydroxypropyl acrylate；The catalyst includes hexamethylenetetramine and quinoline, and the polymerization inhibitor includes 1,4-benzoquinone and p-hydroxyanisole.The advantage of the invention is that：Reaction temperature is low, feed stock conversion is high, byproduct of reaction is few.
Description
Technical field
The present invention relates to field of chemical technology, are more particularly to a kind of preparation side of (methyl) hydroxypropyl acrylate
Method.
Background technology
(methyl) hydroxypropyl acrylate is a kind of important industrial chemicals, due to different carbon chain double bond, hydroxyl and ester
The unique texture of base, can be through homopolymerization and copolymerization multiple polymers as polymerized monomer, and such polymer bonding is securely, no
It easily peels off, is flexible and flexible at room temperature, while there is good water resistance, therefore being widely used in synthesizing (methyl) propylene
Acid resin, light-cured resin, optical resin, coating etc..
It is that (methyl) acrylic acid and propylene oxide are being catalyzed that industrial production (methyl) hydroxypropyl acrylate, which mainly has, at present
Ring-opening reaction is carried out under the action of agent to be made.Known catalyst mainly has following a few classes：1. chromium-based catalysts, the catalysis of 2. iron systems
There are reaction temperatures for agent, 3. amines catalysts, 4. multiplex catalysts, but the reaction occurred under the action of above-mentioned catalyst
High, the shortcomings of feed stock conversion is low, byproduct of reaction is more, high to equipment requirement.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of high (methyl) the acrylic acid hydroxypropyl of feed stock conversion
The preparation method of ester.
The present invention is to solve above-mentioned technical problem by the following technical programs：
A kind of preparation method of (methyl) hydroxypropyl acrylate, includes the following steps：Make (methyl) third at 60~80 DEG C
Olefin(e) acid and propylene oxide are with 1:1~1.5 molar ratio is reacted in a kettle in the presence of catalyst and polymerization inhibitor, system
Crude product (methyl) hydroxypropyl acrylate is obtained, crude product (methyl) hydroxypropyl acrylate is sent into short-path distillation kettle and carries out short distance essence
It evaporates, finished product (methyl) hydroxypropyl acrylate；
The catalyst includes hexamethylenetetramine and quinoline, and the polymerization inhibitor includes 1,4-benzoquinone and p-hydroxyanisole.
Wherein, (methyl) acrylic acid refers to acrylic or methacrylic acid, (methyl) hydroxypropyl acrylate refer to hydroxypropyl acrylate or
Hydroxy propyl methacrylate.
Preferably, the mass ratio of hexamethylenetetramine and quinoline is 2~4:1；The quality of 1,4-benzoquinone and p-hydroxyanisole
Than being 1:2~4.
Preferably, the mass ratio of hexamethylenetetramine and quinoline is 3:1；1,4-benzoquinone and the mass ratio of p-hydroxyanisole are
1:3。
Preferably, the dosage of the catalyst is 0.1~0.5wt%, and the dosage of the polymerization inhibitor is 0.2~0.6wt%,
The wt% is with the total weight of (methyl) acrylic acid and propylene oxide.
Preferably, the dosage of the catalyst is 0.2~0.4wt%, and the dosage of the polymerization inhibitor is 0.3~0.5wt%,
The wt% is with the total weight of (methyl) acrylic acid and propylene oxide.
Preferably, the temperature of the reaction is 70 DEG C.
Preferably, the time of the reaction is 2~4 hours.
Preferably, the operating temperature of the short-path distillation kettle is 50~70 DEG C, operating pressure is -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, improves the conversion ratio of raw material, and byproduct of reaction is reduced.
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
Into stirring-type reaction kettle, addition 860g methacrylic acids, 3.57g hexamethylenetetramines and 1.12g quinoline, which are used as, urges
Agent, 1.59g 1,4-benzoquinone and 4.76g p-hydroxyanisole are as polymerization inhibitor, the air being passed through in nitrogen replacement reaction kettle, stirring
Uniformly, 40 DEG C are warming up to, 725g propylene oxide is passed through, controlling reaction temperature is 70 DEG C, pressure 5KPa, and reaction obtains after 3 hours
Crude product hydroxy propyl methacrylate is obtained, crude product is sent into short-path distillation kettle and carries out short distance rectifying, the work of short-path distillation kettle is set
As temperature be 60 DEG C, operating pressure be -0.03MPa, short-path distillation kettle bottom discharging be finished product hydroxy propyl methacrylate, side goes out
Material mouth is raffinate, and raffinate is fed again into short-path distillation kettle and carries out short-path distillation, and remaining finished product in raffinate is distilled out,
The conversion ratio of raw material is improved, the hydroxy propyl methacrylate that purity is 98% is obtained.
Embodiment 2
Be added into stirring-type reaction kettle 720g acrylic acid, 3.3g hexamethylenetetramines and 1.1g quinoline as catalyst,
As polymerization inhibitor, the air being passed through in nitrogen replacement reaction kettle stirs evenly for 1.4g 1,4-benzoquinone and 4.3g p-hydroxyanisole, rises
Temperature is passed through 725g propylene oxide to 40 DEG C, and controlling reaction temperature is 70 DEG C, pressure 5KPa, and reaction obtains crude product third after 3 hours
Olefin(e) acid hydroxypropyl acrylate, will crude product be sent into short-path distillation kettle in carry out short distance rectifying, setting short-path distillation kettle operating temperature be 50 DEG C,
Operating pressure is -0.05MPa, and the discharging of short-path distillation kettle bottom is finished product hydroxypropyl acrylate, and side discharge port is raffinate, by raffinate
It is fed again into short-path distillation kettle and carries out short-path distillation, remaining finished product in raffinate is distilled out, improve the conversion ratio of raw material,
Obtain the hydroxypropyl acrylate that purity is 96%.
Embodiment 3
Into stirring-type reaction kettle, addition 860g methacrylic acids, 1.92g hexamethylenetetramines and 0.96g quinoline, which are used as, urges
Agent, 1.44g 1,4-benzoquinone and 2.88g p-hydroxyanisole are as polymerization inhibitor, the air being passed through in nitrogen replacement reaction kettle, stirring
Uniformly, 40 DEG C are warming up to, 580g propylene oxide is passed through, controlling reaction temperature is 60 DEG C, pressure 5KPa, and reaction obtains after 2 hours
Crude product hydroxy propyl methacrylate is obtained, crude product is sent into short-path distillation kettle and carries out short distance rectifying, the work of short-path distillation kettle is set
As temperature be 70 DEG C, operating pressure be -0.01MPa, short-path distillation kettle bottom discharging be finished product hydroxy propyl methacrylate, side goes out
Material mouth is raffinate, and raffinate is fed again into short-path distillation kettle and carries out short-path distillation, and remaining finished product in raffinate is distilled out,
The conversion ratio of raw material is improved, the hydroxy propyl methacrylate that purity is 97% is obtained.
Embodiment 4
720g acrylic acid, 5.08g hexamethylenetetramines and 1.27g quinoline are added into stirring-type reaction kettle as catalysis
Agent, 1.59g 1,4-benzoquinone and 6.36g p-hydroxyanisole are as polymerization inhibitor, the air being passed through in nitrogen replacement reaction kettle, and stirring is equal
It is even, 40 DEG C are warming up to, 870g propylene oxide is passed through, controlling reaction temperature is 80 DEG C, pressure 5KPa, and reaction obtains after 4 hours
Crude product is sent into short-path distillation kettle and carries out short distance rectifying by crude product hydroxypropyl acrylate, and the operating temperature of short-path distillation kettle is arranged
It is -0.04MPa for 65 DEG C, operating pressure, the discharging of short-path distillation kettle bottom is finished product hydroxypropyl acrylate, and side discharge port is residual
Raffinate is fed again into short-path distillation kettle and carries out short-path distillation by liquid, and remaining finished product in raffinate is distilled out, and improves raw material
Conversion ratio, obtain purity be 93% hydroxypropyl acrylate.
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 (8)
1. a kind of preparation method of (methyl) hydroxypropyl acrylate, which is characterized in that include the following steps：Make at 60~80 DEG C
(methyl) acrylic acid and propylene oxide are with 1:1~1.5 molar ratio in the presence of catalyst and polymerization inhibitor in a kettle into
Row reaction, be made crude product (methyl) hydroxypropyl acrylate, by crude product (methyl) hydroxypropyl acrylate be sent into short-path distillation kettle in into
Row short distance rectifying, finished product (methyl) hydroxypropyl acrylate；
The catalyst includes hexamethylenetetramine and quinoline, and the polymerization inhibitor includes 1,4-benzoquinone and p-hydroxyanisole.
2. the preparation method of (methyl) hydroxypropyl acrylate according to claim 1, which is characterized in that hexamethylenetetramine
Mass ratio with quinoline is 2~4:1；1,4-benzoquinone and the mass ratio of p-hydroxyanisole are 1:2~4.
3. the preparation method of (methyl) hydroxypropyl acrylate according to claim 2, which is characterized in that hexamethylenetetramine
Mass ratio with quinoline is 3:1；1,4-benzoquinone and the mass ratio of p-hydroxyanisole are 1:3.
4. the preparation method of (methyl) hydroxypropyl acrylate according to claim 1, which is characterized in that the catalyst
Dosage is 0.1~0.5wt%, and the dosage of the polymerization inhibitor is 0.2~0.6wt%, and the wt% is with (methyl) acrylic acid and ring
The total weight of Ethylene Oxide.
5. the preparation method of (methyl) hydroxypropyl acrylate according to claim 4, which is characterized in that the catalyst
Dosage is 0.2~0.4wt%, and the dosage of the polymerization inhibitor is 0.3~0.5wt%, and the wt% is with (methyl) acrylic acid and ring
The total weight of Ethylene Oxide.
6. the preparation method of (methyl) hydroxypropyl acrylate according to claim 1, which is characterized in that the temperature of the reaction
Degree is 70 DEG C.
7. the preparation method of (methyl) hydroxypropyl acrylate according to claim 1, which is characterized in that the reaction when
Between be 2~4 hours.
8. the preparation method of (methyl) hydroxypropyl acrylate according to claim 1, which is characterized in that the short-path distillation
The operating temperature of kettle is 50~70 DEG C, operating pressure is -0.05~-0.01Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810058551.1A CN108409566A (en) | 2018-01-22 | 2018-01-22 | It is a kind of（Methyl）The preparation method of hydroxypropyl acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810058551.1A CN108409566A (en) | 2018-01-22 | 2018-01-22 | It is a kind of（Methyl）The preparation method of hydroxypropyl acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108409566A true CN108409566A (en) | 2018-08-17 |
Family
ID=63125985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810058551.1A Pending CN108409566A (en) | 2018-01-22 | 2018-01-22 | It is a kind of（Methyl）The preparation method of hydroxypropyl acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108409566A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062677A (en) * | 2020-08-21 | 2020-12-11 | 温州国仕邦高分子材料有限公司 | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof |
| CN114835578A (en) * | 2022-06-10 | 2022-08-02 | 安徽三禾化学科技有限公司 | Preparation method of hydroxypropyl acrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524343A (en) * | 2013-09-27 | 2014-01-22 | 常州大学 | Method for synthesizing hydroxy-propyl acrylate |
| CN105272851A (en) * | 2014-07-14 | 2016-01-27 | 万华化学集团股份有限公司 | Preparation method of hydroxyethyl (meth)acrylate |
-
2018
- 2018-01-22 CN CN201810058551.1A patent/CN108409566A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524343A (en) * | 2013-09-27 | 2014-01-22 | 常州大学 | Method for synthesizing hydroxy-propyl acrylate |
| CN105272851A (en) * | 2014-07-14 | 2016-01-27 | 万华化学集团股份有限公司 | Preparation method of hydroxyethyl (meth)acrylate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062677A (en) * | 2020-08-21 | 2020-12-11 | 温州国仕邦高分子材料有限公司 | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof |
| CN112062677B (en) * | 2020-08-21 | 2022-12-23 | 温州国仕邦高分子材料有限公司 | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof |
| CN114835578A (en) * | 2022-06-10 | 2022-08-02 | 安徽三禾化学科技有限公司 | Preparation method of hydroxypropyl acrylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3350234B1 (en) | Methods of preparing a catalyst | |
| EP3257880A1 (en) | Organic zinc compound comprising polyolefin-polystyrene block copolymer, and method for preparing same | |
| TWI471291B (en) | Process for preparing a carboxamide from a carbonyl compound and hydrogen cyanide | |
| KR20170013349A (en) | Procatalyst for polymerization of olefins comprising a monoester and an amidobenzoate internal donor | |
| EP2834280B1 (en) | Ethylene polymerization process using an inhibitor | |
| KR20170015386A (en) | Procatalyst for polymerization of olefins | |
| EP2834279B1 (en) | High-pressure radical ethylene polymerization process in which ethylene is polymerized with a specific polyunsaturated olefin grade | |
| CN108409566A (en) | It is a kind of（Methyl）The preparation method of hydroxypropyl acrylate | |
| CN1278832A (en) | Process for the gas phase polymerisation of olefins | |
| EP2647650B1 (en) | High-pressure radical ethylene co-polymerization process with a reduced temperature of the reaction mixture prior to introduction into the reaction zone | |
| EP2935354B1 (en) | Process for the polymerization of propylene | |
| CN105348443B (en) | The preparation method of synthesizing pentadiene Petropols catalyst system and catalyzing and m-pentadiene petro-resin | |
| CN104447672A (en) | Method for synthesizing epsilon-caprolactone by using active carbon immobilized heteropoly acid | |
| CN112062678A (en) | Method for preventing polymerization in tert-butyl acrylate production process | |
| CN107312169A (en) | A kind of polyketone manufacturing technique method and its process unit | |
| CN108409565A (en) | It is a kind of（Methyl）The preparation method of hydroxy-ethyl acrylate | |
| CN112679721A (en) | Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol | |
| CN108003533A (en) | A kind of high glaze acryl plates and preparation method thereof | |
| US10479856B2 (en) | Manufacturing method for propylene block copolymer | |
| EP4032920A1 (en) | Method for manufacturing vinyl chloride-acryl copolymer latex | |
| EP4032919A1 (en) | Method for preparing vinyl chloride-vinyl acetate copolymer latex | |
| CN110511532A (en) | A kind of maleic acid anhydride-propenoic acid ester copolymer phenol-formaldehyde resin modified | |
| CN114599683B (en) | Method for producing vinyl chloride-acrylic acid copolymer latex | |
| CN109422827A (en) | Major catalyst component, preparation method and catalyst system for solwution method vinyl polymerization | |
| CN108129840A (en) | A kind of anti-aging acryl plates and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180817 |