CN1687006A - 2-methacrylic acid-3-chlorine-2-propylene - Google Patents
2-methacrylic acid-3-chlorine-2-propylene Download PDFInfo
- Publication number
- CN1687006A CN1687006A CN 200510046147 CN200510046147A CN1687006A CN 1687006 A CN1687006 A CN 1687006A CN 200510046147 CN200510046147 CN 200510046147 CN 200510046147 A CN200510046147 A CN 200510046147A CN 1687006 A CN1687006 A CN 1687006A
- Authority
- CN
- China
- Prior art keywords
- methacrylic acid
- chloro
- product
- isomer
- chlorine
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a 3-chloro-2-propenyl 2-methacrylate, belonging to a new-type acrylate monomer, including cis-and trans-isomers. Said invention also provide their stricture formulas respectively. Said product can be synthesized by using DD mixture as one main raw materials, and said product can be used for producing high-malecular resin material, and can be used as cross-linking agent of thermoplastic resin and paint modifying agent.
Description
The technical field is as follows:
the invention relates to acrylic ester, in particular to 2-methacrylic acid-3-chlorine-2-acrylic ester.
Background art:
acrylic ester is an important industrial derivative of propylene, the demand of China for acrylic acid and esters thereof in 2005 exceeds 40 ten thousand tons, and the acrylic ester is mainly used in the fields of chemical fibers, textiles, coatings, leather and adhesives. The production capacity and the yield of acrylic ester in China are small, and the production capacity is expanded, the product quality is improved and the application field is expanded through technical improvement according to the industrial characteristics.
One of the main synthetic raw materials of the product of the invention is 1, 3-dichloropropene (including cis-isomer and trans-isomer) or a hydrolysate thereof, namely 3-chloroallyl alcohol (including cis-isomer and trans-isomer), the invention particularly focuses on taking DD mixed agent as the source of 1, 3-dichloropropene, separates 1, 2-dichloropropane in the DD mixed agent while synthesizing novel acrylate monomers, and solves the problem of comprehensive utilization of the DD mixed agent.
The DD mixing agent is a high-boiling point byproduct generated in the production of 3-chloropropene by a propylene thermal chlorination method, the main components of the DD mixing agent are 1, 2-dichloropropane and 1, 3-dichloropropene (including cis-isomer and trans-isomer), and the 3-chloropropene is mainly used for producing epichlorohydrin. At present, the production capacity of epichlorohydrin in China is 4.5 ten thousand tons per year, about 230 kilograms of DD mixed agent is generated when one ton of epichlorohydrin is produced, and nearly ten thousand tons of DD mixed agent are generated every year. And the production device of the epichlorohydrin is increased, and the generation amount of the DD mixing agent is correspondingly increased, so that the problem of treatment and utilization of the DD mixing agent is to be solved. The development of a more effective comprehensive utilization way of the DD mixed agent has important practical significance for reducing environmental pollution and improving the utilization rate of resources.
The 2-methacrylic acid-3-chlorine-2-acrylate is a novel acrylate monomer, is different from existing allyl methacrylate in molecular structure and synthetic raw materials, and has no report on related name, structural formula and synthetic method of the product.
The invention content is as follows:
the invention utilizes 1, 3-dichloropropene as one of the main raw materials, particularly pays attention to the fact that DD mixed agent is used as the source of the 1, 3-dichloropropene, and 2-methacrylic acid-3-chloro-2-propenyl ester is synthesized by esterification reaction between methacrylate and the 1, 3-dichloropropene, thereby achieving the purposes of reasonably utilizing resources and enriching the variety of acrylate monomers.
The following provides a method for preparing the product of the present invention.
The mixed agent of methacrylic acid, alkali, polymerization inhibitor and catalyst and DD is used to prepare 1, 3-dichloropropene (ClCH ═ CHCH)2Cl) will participate in the esterification reactionThe 2-methacrylic acid-3-chlorine-2-propylene ester is generated, and the basic reaction formula is as follows:
the synthesized 2-methacrylic acid-3-chlorine-2-propylene ester comprises cis-isomer and trans-isomer, and the structural formulas are respectively
And
the preparation of the 2-methacrylic acid-3-chlorine-2-propylene ester taking the DD mixed agent as the main raw material comprises four process steps: raw material pretreatment, catalytic esterification reaction, product separation and product refining.
1. Feedstock and pretreatment of feedstock
The DD mixture which is one of the main raw materials in the invention is an industrial byproduct, namely dark brown oily liquid, the contents of main components 1, 2-dichloropropane and 1, 3-dichloropropene (including cis-isomer and trans-isomer) are more than 95 percent, and a small amount of 3-chloropropene, carbonized impurities, water and the like are also contained. Therefore, the DD mixed agent needs to be dehydrated and simply distilled to remove impurities, and 97-100 ℃ fractions are received. Because the content of the 1, 3-dichloropropene in each DD mixed agent is different, the content of each DD mixed agent needs to be analyzed by gas chromatography, and the DD mixed agent is used as the basis for the proportion of the reaction raw materials, and generally comprises 37-75% of 1, 2-dichloropropane and 63-23% of 1, 3-dichloropropene (including cis-isomer and trans-isomer).
The synthetic raw material of the 2-methacrylic acid-3-chlorine-2-propylene ester can directly adopt 1, 3-dichloropropene (ClCH) without adopting DD mixing agent2CH ═ CHCl) or its hydrolyzate 3-chloroallyl alcohol (ClCH ═ CHCH)2OH)。
The invention adopts methacrylic acid as another main raw material, and industrial products of the methacrylic acid are refined by reduced pressure distillation before use to remove polymers and impurities possibly contained, and a proper amount of polymerization inhibitor is added to prevent further polymerization.
The polymerization inhibitor for methacrylic acid in the present invention includes various polymerization inhibitors for radical polymerization such as hydroquinone, p-hydroxyanisole or phenothiazine, and preferably a nitrogen radical type polymerization inhibitor such as DPPH. The polymerization inhibitor needs to be added into the methacrylic acid before distillation, and the dosage of the polymerization inhibitor is 0.001-0.1% of the mass of the methacrylic acid.
The alkali used in the preparation process of the product can be sodium hydroxide, potassium hydroxide or other alkaline compounds, and can also be aqueous solution of the corresponding alkali. The molar ratio of the methacrylic acid to the alkali is 1: 1-1.5.
The catalyst adopted in the catalytic esterification reaction is triethylamine, cuprous chloride or a phase transfer catalyst, such as polyethylene glycol and various quaternary ammonium salts, and the dosage of the catalyst is 1-10% of the mass of methacrylic acid.
2. Catalytic esterification reaction
The catalytic esterification process of the present invention may be a two-step process or a one-step process.
The two-step method is that alkali and methacrylic acid are neutralized to prepare corresponding methacrylate, then the generated salt is taken as a raw material of esterification reaction, the raw material is mixed with DD mixing agent, catalyst and polymerization inhibitor in an esterification reactor, and the mixture is stirred and heated to the reaction temperature to carry out catalytic esterification reaction. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
The one-step method is that DD mixed agent, methacrylic acid, polymerization inhibitor, alkali and catalyst are added into an esterification reactor in sequence according to a certain proportion, stirred and heated to the reaction temperature, and catalytic esterification reaction is carried out. The reaction temperature can be 60-100 ℃, the reaction time can be 3-8 hours, and the reaction is carried out under normal pressure.
3. Product separation
After the catalytic esterification reaction is finished, the system is cooled to room temperature and stands, inorganic salt generated by the reaction is precipitated and can be directly filtered and separated out; or adding a proper amount of water into the system to dissolve the generated inorganic salt, standing for layering, and removing the water phase. If the organic phase contains a small amount of water, a proper amount of drying agent such as anhydrous magnesium sulfate can be added for drying.
The DD mixed agent is adopted as a raw material, the desalted organic phase mainly contains 1, 2-dichloropropane and 2-methacrylic acid-3-chloro-2-propenyl ester, distillation is carried out at normal pressure, a fraction at 95-100 ℃ is collected to obtain the 1, 2-dichloropropane, the separation rate is 80-100%, the purity is 95-100%, and meanwhile, the organic phase mainly containing the 2-methacrylic acid-3-chloro-2-propenyl ester is obtained.
4. Product refinement
The 2-methacrylic acid-3-chlorine-2-propenyl ester obtained by the process also contains impurities such as polymers and the like, has low purity, can be distilled and refined under the vacuum degree of 0.5-3 KPa, and collects main fractions, namely the 2-methacrylic acid-3-chlorine-2-propenyl ester, wherein the yield is more than 70% and the purity is more than 95%.
The component content of the DD mixture and the purity of the 2-methacrylic acid-3-chloro-2-propenyl ester can be analyzed anddetermined by a gas chromatograph.
The product 2-methacrylic acid-3-chlorine-2-propylene ester is a novel acrylate monomer, and can be used for producing a high polymer resin material by utilizing the self-polymerization or the copolymerization reaction with other monomers. For example, the product is initiated to polymerize at about 80 ℃ under the action of a free radical initiator benzoyl peroxide to generate an elastic resin which can swell but can not be dissolved in aromatic hydrocarbon and halogenated hydrocarbon, can not be melted when heated and can be decomposed at the temperature of more than 150 ℃. The product contains double olefinic bonds, and can be used as thermoplastic resin crosslinking agent and coating modifier. The invention enriches the types of acrylate monomers. The synthesis of the product of the invention can adopt the cheap DD mixing agent as the main raw material, thereby opening up a way for producing the low-cost acrylic ester.
The specific implementation mode is as follows:
example 1
The DD mixture was dehydrated and briefly distilled to remove impurities, and the contents of its components were analyzed by gas chromatography. The methacrylic acid is refined by reduced pressure distillation, polymers and impurities which may be contained are removed, and a proper amount of polymerization inhibitor is added to prevent the polymerization.
After a stirring device, a water separator and a condenser are arranged on a three-mouth bottle, 43g (0.5mol) of methacrylic acid and 0.04g of polymerization inhibitor DPPH0 are added, stirred and cooled, and 20g (0.5mol) of sodium hydroxide is added for neutralization. Then, the product was azeotropically dehydrated with benzene and dried in vacuo to obtain about 54g of sodium methacrylate.
A stirring device, a condenser and a thermometer are arranged on a 500ml three-mouth bottle, and 241.3g (containing 23 percent of 1, 3-dichloropropene and 0.5mol) of DD mixed agent, 54g (0.5mol) of sodium methacrylate, 0.04g of DPPH0 and 3ml of triethylamine are added in turn under stirring. Heating the mixture to 85-90 ℃ in an oil bath, and reacting for 5 hours at constant temperature. After the esterification reaction is finished, cooling to room temperature, and filtering to remove the generated inorganic salt precipitate. (or adding water to dissolve inorganic salt, standing for layering, and removing a water phase.) adding a proper amount of anhydrous magnesium sulfate into an organic phase to remove residual water, adding 0.1g of hydroquinone, distilling at normal pressure, and collecting a fraction at 95-100 ℃ to obtain the 1, 2-dichloropropane. The remainder was distilled and refined under a vacuum of 1.3KPa, the main fraction was collected, i.e. 2-methacrylic acid-3-chloro-2-propenyl ester, the purity was 97.0% by gas chromatograph analysis, the yield was calculated to be 75.6%.
Example 2
The methacrylic acid raw material pretreatment process was the same as above.
After a stirring device, a water separator and a condenser are arranged on a 500ml three-necked bottle, 55.5g (0.5mol) of 1, 3-dichloropropene, 43g (0.5mol) of methacrylic acid, 0.04g of DPPH0, 20g (0.5mol) of sodium hydroxide and 2.5ml of triethylamine are sequentially added under stirring, the mixture is stirred and heated, the reaction temperature is 85-90 ℃, the reaction time is 5 hours, inorganic salts are separated and removed after the reaction is finished, and 2-methacrylic acid-3-chloro-2-propenyl ester is obtained through rectification separation, wherein the yield is 70.8%.
Example 3
After a stirring device,a water separator and a thermometer are arranged on a three-mouth bottle, 92.5g (1mol) of 3-chloroallyl alcohol, 86g (1mol) of 2-methacrylic acid, 0.1g of polymerization inhibitor and a proper amount of water carrying agent are added, the mixture reacts for 5 hours at a reflux temperature, and 2-methacrylic acid-3-chloro-2-allyl ester is obtained through rectification separation, wherein the yield is 70.6%.
The 2-methacrylic acid-3-chlorine-2-propenyl ester synthesized in the embodiments 1, 2 and 3 comprises cis-isomer and trans-isomer, and the structural formulas are respectively
And
Claims (3)
1. 2-methacrylic acid-3-chloro-2-propenyl ester, comprising cis-isomer and trans-isomer, the structural formulas of which are respectively
And
2. the 2-methacrylic acid-3-chloro-2-propenyl ester according to claim 1, characterized in that the 2-methacrylic acid-3-chloro-2-propenyl ester is useful for the preparation of polymeric resin materials, and also as a crosslinking agent for thermoplastic resins, a coating modifier.
3. The 3-chloro-2-propenoic acid-2-methacrylate as claimed in claim 1, wherein 1, 3-dichloropropene, 3-chloroallyl alcohol or DD mixture which is a chemical by-product can be used as one of the raw materials for the synthesis.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510046147 CN1687006A (en) | 2005-03-31 | 2005-03-31 | 2-methacrylic acid-3-chlorine-2-propylene |
| CNB2006102003033A CN100402476C (en) | 2005-03-31 | 2006-03-30 | Method of separating 1,2-dichloropropane with DD mixture |
| CNB2006102003029A CN100402486C (en) | 2005-03-31 | 2006-03-30 | Process for preparing acrylic acid-3-chloro-2-acrylate by using DD mixed agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510046147 CN1687006A (en) | 2005-03-31 | 2005-03-31 | 2-methacrylic acid-3-chlorine-2-propylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1687006A true CN1687006A (en) | 2005-10-26 |
Family
ID=35305048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510046147 Pending CN1687006A (en) | 2005-03-31 | 2005-03-31 | 2-methacrylic acid-3-chlorine-2-propylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1687006A (en) |
-
2005
- 2005-03-31 CN CN 200510046147 patent/CN1687006A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013059473A2 (en) | Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom | |
| CN1391552A (en) | Transesterification method for making cyanoacrylates | |
| CN107318266B (en) | Process for preparing (meth) acrylate group-containing benzophenones for optical adhesive use and optical adhesive composition | |
| CN113248463B (en) | Preparation method of tung oil-based fatty acid modified monomer, prepared tung oil-based fatty acid modified monomer and application thereof | |
| CN1300184C (en) | Process FPR purification of alkoxystyrene polymers | |
| CN1687007A (en) | Crylic acid-3-chlorine-2-propylene | |
| KR960000038B1 (en) | Novel polymerizable vinyl monomers and vinyl resins prepared therefrom | |
| CN1687006A (en) | 2-methacrylic acid-3-chlorine-2-propylene | |
| CN1847205A (en) | Method of separating 1,2-dichloropropane with DD mixture | |
| CN111196793A (en) | Preparation method of 2, 5-furan dicarboxylic acid dialkyl ester | |
| CN1019970C (en) | Method for recovering acrylic acid and/or ethyl acrylate from black acid | |
| US5869732A (en) | Process for producing tricyanoethylated pentaerythritol | |
| CN1687001A (en) | Method for esterifying organic acid | |
| CN1687005A (en) | Method for preparing acrylic ester and separation 1,2-dichloropropane by using DD mixing agent | |
| CN1840520A (en) | Process for preparing acrylic acid-3-chloro-2-acrylate by using DD mixed agent | |
| CN1028526C (en) | Process for preparing mercapto-terminated hydroxyamides | |
| CN1946668A (en) | Process for producing fluorinated acrylic ester | |
| JPH0713050B2 (en) | Method for producing dimethylaminoethyl acrylate | |
| JP3885249B2 (en) | Purification method of glycidyl (meth) acrylate | |
| US20060009653A1 (en) | 3-Hydroxypropyl ester of 2-trifluoromethylacrylic acid and process for producing same | |
| JPS63215720A (en) | Production of functional group-terminated lactone polymer | |
| CN1281586C (en) | Carbazyl dithio formate RAFT reagent and its preparation method and use | |
| CN109704962A (en) | A kind of more acrylate monomers of water soluble polyhydroxy and preparation method thereof | |
| JP2611614B2 (en) | Method for producing lactone-modified acrylate or methacrylate | |
| CN111302938B (en) | Synthesis method of trimethylolpropane triacrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |