CN104592005A - Method of preparing acryloyl chloride by virtue of continuous method - Google Patents
Method of preparing acryloyl chloride by virtue of continuous method Download PDFInfo
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- CN104592005A CN104592005A CN201510006437.0A CN201510006437A CN104592005A CN 104592005 A CN104592005 A CN 104592005A CN 201510006437 A CN201510006437 A CN 201510006437A CN 104592005 A CN104592005 A CN 104592005A
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- acrylate chloride
- vinylformic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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Abstract
The invention discloses a method of preparing acryloyl chloride by virtue of a continuous method. The method comprises the following steps: respectively weighing a first batch of acrylic acid mass and inhibitor mass as well as a second batch of acrylic acid mass and inhibitor mass, wherein the mass of the inhibitor accounts 0.5-1.0 percent of the mass of acrylic acid in the first batch; then adding the first batch of acrylic acid into a reaction vessel, adding the inhibitor, stirring at 200-250rap/min, heating to 78-88 DEG C/200-500mm Hg, then adding the second batch of acrylic acid and thionyl chloride, cooling acryloyl chloride generated by reaction by virtue of a condenser, and collecting acryloyl chloride under reduced pressure of 200-500mmHg. According to the method disclosed by the invention, at certain temperature and pressure, acryloyl chloride is collected while the materials are fed, so that the phenomenon that the side reactions including polymerization and addition are easily caused when a target product stays in a reaction system with relatively high temperature for a long time is avoided, the quality of the product is greatly improved, and the yield of the product is greatly increased.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of acrylate chloride, a kind of continuous processing prepares the method for acrylate chloride specifically.
Background technology
Acrylate chloride chemical property is active, and number of chemical reaction can occur, and is important organic synthesis intermediate.It has people's acrylate chloride and polyether reactant to prepare macromolecule member material mainly for the preparation of special acrylic acid esters product and acrylamide series products in recent years.Existing continuous processing prepares the method for acrylate chloride, the acrylate chloride yield obtained due to it and purity lower, and subsequent technique is loaded down with trivial details, and therefore, the technique of current preparation of industrialization acrylate chloride is little.
Summary of the invention
For the defect existed in above-mentioned prior art, technical problem to be solved by this invention is to provide a kind of method that continuous processing prepares acrylate chloride, the method that described this continuous processing prepares acrylate chloride will solve the complex process preparing acrylate chloride of the prior art, the technical problem that product purity, yield are low.
A kind of continuous processing of the present invention prepares the method for acrylate chloride, comprise the step that takes first vinylformic acid quality, a step taking stopper quality, a step taking second batch vinylformic acid quality, a step taking sulfur oxychloride quality, the quality of described stopper is 0.5 ~ 1.0% of described first vinylformic acid quality, then first described vinylformic acid is added in a reaction vessel, and add described stopper, under 200 ~ 250rap/min stirs, be heated to 78 ~ 88 DEG C/200 ~ 500mmHg, drip second batch vinylformic acid and sulfur oxychloride again, the acrylate chloride that reaction generates cools through condenser and collects under 200 ~ 500mmHg decompression.
Further, described stopper is Resorcinol.
Further, described second batch vinylformic acid and sulfur oxychloride drop in reaction vessel with equimolar amount simultaneously, and acrylic acid rate of addition is 1.2 ~ 2.2g/min; The rate of addition of sulfur oxychloride is 2 ~ 4g/min.
Further, described reaction vessel be one with thermometer, agitator, constant pressure funnel, still head, craspedodrome prolong, connect the container of skirt, receiving flask and gas absorption bottle.
Further, the temperature of the cooling fluid in described craspedodrome prolong controls between-15 ~ 10 DEG C.
Further, described reaction vessel connects a receiving flask by connecing skirt, described receiving flask is placed in the cold trap of a temperature between-15 ~ 10 DEG C, add in described gas absorption bottle have mass percent concentration be 20 ~ 30% alkaline solution, for collecting hydrogenchloride, concrete, described alkaline solution is sodium hydroxide or sodium carbonate solution.
Principle of the present invention is: be first added in reaction vessel with a certain amount of raw material propylene acid, and rely on this part vinylformic acid through heating, the temperature of reaction system is maintained 78 ~ 88 DEG C (at 200 ~ 500mmHg), this part vinylformic acid is also reactant simultaneously.After sulfur oxychloride is added to above-mentioned system, sulfur oxychloride and vinylformic acid reaction generate acrylate chloride (under normal pressure boiling point 72 DEG C) and hydrogenchloride, because of in negative pressure system and the temperature of reaction system again higher than the boiling point of acrylate chloride, so distillate reaction system rapidly after condensation, the hydrogen chloride gas alkali liquor absorption produced in reaction once the acrylate chloride of reaction generation.In the removal process of acrylate chloride, because condenser system temperature is lower, therefore, the hydrogen chloride gas generation addition reaction of acrylate chloride and effusion is avoided.Another part of vinylformic acid simultaneously dripped with sulfur oxychloride is the acrylic acid amount reacted away in balanced reaction system.In order to realize the preparation of continuous acrylate chloride, the balance adding vinylformic acid in reaction system, sulfur oxychloride and acrylate chloride quantity of distillate need be controlled well.
The present invention compares with prior art, and its technical progress is significant.Present invention employs easier preparation and be separated into method integrally, obtain the acrylate chloride of higher yields and purity, the method is under certain temperature certain pressure, feed in raw material while collect acrylate chloride, avoid object product to rest on for a long time in the reaction system of comparative high temperature and easily cause the side reactions such as polymerization, addition, greatly increase the quality of product and the yield of product, can 86% be reached in the yield of sulfur oxychloride acrylate chloride.Method of the present invention can continuous production acrylate chloride, provides guarantee for realizing suitability for industrialized production.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but do not limit the present invention.
embodiment 1
First the vinylformic acid of 250mL and the stopper of 2.0g are added in the 500mL four-hole boiling flask with thermometer, agitator, constant pressure funnel and Distallation systm (comprising still head, straight cold finger and receiving flask), when being heated to 85 DEG C/200mmHg under stirring, drip 250g sulfur oxychloride (purity is greater than 95%) and 150g vinylformic acid (purity is greater than 99%).Simultaneously, acrylate chloride is collected in distillation, its yield in the yield of sulfur oxychloride acrylate chloride reach 86% (sulfur oxychloride and vinylformic acid reaction by etc. mole to carry out, in the present reaction, vinylformic acid is excessive, so will calculate with the input amount of sulfur oxychloride when calculating productive rate and the yield of product propylene acyl chlorides.)。(note: this device is the reactor that a reaction is integrated with distillation, and the temperature of the cooling fluid in its craspedodrome prolong controls at-15 ~ 10 DEG C, and receiving flask is placed in-15 ~ 10 DEG C of cold traps.）
embodiment 2
First the vinylformic acid of 250mL and the stopper of 2.0g are added in the 500mL four-hole boiling flask with thermometer, agitator, constant pressure funnel and Distallation systm, when being heated to 85 DEG C/300mmHg under stirring, drip 250g sulfur oxychloride (purity is greater than 95%) and 150g vinylformic acid (purity is greater than 99%).Meanwhile, acrylate chloride is collected in distillation, and its yield counts 75 ~ 80% with sulfur oxychloride.
embodiment 3
First the vinylformic acid of 250mL and the stopper of 2.0g are added in the 500mL four-hole boiling flask with thermometer, agitator, constant pressure funnel and Distallation systm, when being heated to 85 DEG C/500mmHg under stirring, drip 250g sulfur oxychloride (purity is greater than 95%) and 150g vinylformic acid (purity is greater than 99%).Meanwhile, acrylate chloride is collected in distillation, and its yield is counted with sulfur oxychloride and is less than 50%.
Under acrylate chloride normal pressure, boiling point is 72 DEG C, and vacuum tightness is higher, and boiling point is lower.In embodiment 2 and 3, vacuum tightness compares in embodiment 1 and wants high, generates like this once acrylate chloride, because the acrylate chloride boiling point steamed is low, having a narrow range of temperature between itself and cooling fluid, it not easily cools, a large amount of acrylate chlorides is drawn in alkali liquor absorption system and vacuum pump, and acryloyl chlorine dose is reduced.
embodiment 4
First the vinylformic acid of 250mL and the stopper of 2.0g are added in the 500mL four-hole boiling flask with thermometer, agitator, constant pressure funnel and Distallation systm, when being heated to 85 DEG C under stirring, drip 250g sulfur oxychloride (purity is greater than 95%) and 150g vinylformic acid (purity is greater than 99%).Meanwhile, acrylate chloride is collected in distillation, and its yield is counted with sulfur oxychloride and is less than 30%.In the present embodiment, because reacting at ambient pressure, the acrylate chloride (boiling point 72 DEG C) generated steams (the temperature of system 85 DEG C not in time from reaction system, because the temperature difference is less, 85-72=13 DEG C), make a part of acrylate chloride and its hydrogenchloride simultaneously generated addition reaction can occur like this, decrease product propylene acyl chlorides.
embodiment 5
First the vinylformic acid of 250mL and the stopper of 2.0g are added in the 500mL four-hole boiling flask with thermometer, agitator, constant pressure funnel and Distallation systm, when being heated to 75 DEG C under stirring, drip 250g sulfur oxychloride (purity is greater than 95%) and 150g vinylformic acid (purity is greater than 99%).Meanwhile, acrylate chloride is collected in distillation, and its yield is counted with sulfur oxychloride and is less than 5%.In the present embodiment, because reacting at ambient pressure, the acrylate chloride (boiling point 72 DEG C) generated steams (the temperature of system 75 DEG C more not in time from reaction system, because the temperature difference is less, 75-72=3 DEG C), make a large amount of acrylate chlorides and its hydrogenchloride simultaneously generated addition reaction can occur like this, decrease product propylene acyl chlorides.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (6)
1. a continuous processing prepares the method for acrylate chloride, it is characterized in that: comprise the step that takes first vinylformic acid quality, a step taking stopper quality, a step taking second batch vinylformic acid quality, a step taking sulfur oxychloride quality, the quality of described stopper is 0.5 ~ 1.0% of described first vinylformic acid quality, then first described vinylformic acid is added in a reaction vessel, and add described stopper, under 200 ~ 250rap/min stirs, be heated to 78 ~ 88 DEG C/200 ~ 500mmHg, drip second batch vinylformic acid and sulfur oxychloride again, the acrylate chloride that reaction generates cools through condenser and collects under 200 ~ 500mmHg decompression.
2. a kind of continuous processing as claimed in claim 1 prepares the method for acrylate chloride, it is characterized in that: described stopper is Resorcinol.
3. a kind of continuous processing as claimed in claim 1 prepares the method for acrylate chloride, it is characterized in that: described second batch vinylformic acid and sulfur oxychloride drop in reaction vessel with equimolar amount simultaneously, and acrylic acid rate of addition is 1.2 ~ 2.2g/min; The rate of addition of sulfur oxychloride is 2 ~ 4g/min.
4. a kind of continuous processing as claimed in claim 1 prepares the method for acrylate chloride, it is characterized in that: described reaction vessel be one with thermometer, agitator, constant pressure funnel, still head, craspedodrome prolong, connect the container of skirt, receiving flask and gas absorption bottle.
5. a kind of continuous processing as claimed in claim 4 prepares the method for acrylate chloride, it is characterized in that: the temperature of the cooling fluid in described craspedodrome prolong controls between-15 ~ 10 DEG C.
6. a kind of continuous processing as claimed in claim 4 prepares the method for acrylate chloride, it is characterized in that: described receiving flask is placed in the cold trap of a temperature between-15 ~ 10 DEG C, add in described gas absorption bottle have mass percent concentration be 20 ~ 30% alkaline solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510006437.0A CN104592005A (en) | 2015-01-07 | 2015-01-07 | Method of preparing acryloyl chloride by virtue of continuous method |
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| CN201510006437.0A CN104592005A (en) | 2015-01-07 | 2015-01-07 | Method of preparing acryloyl chloride by virtue of continuous method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553526A (en) * | 2018-12-18 | 2019-04-02 | 杭州盛弗泰新材料科技有限公司 | A kind of continuous producing method of acryloyl chloride |
| CN115612158A (en) * | 2022-11-16 | 2023-01-17 | 山东华业包装科技股份有限公司 | Glassine-like polypropylene film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066923A (en) * | 2007-05-28 | 2007-11-07 | 无锡百川化工股份有限公司 | Process of producing trihydroxy methyl propane acrylat with high purity |
| CN101781205A (en) * | 2010-03-30 | 2010-07-21 | 丽水市南明化工有限公司 | Method for synthesizing substitutional crylic acid phenyl ester |
-
2015
- 2015-01-07 CN CN201510006437.0A patent/CN104592005A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066923A (en) * | 2007-05-28 | 2007-11-07 | 无锡百川化工股份有限公司 | Process of producing trihydroxy methyl propane acrylat with high purity |
| CN101781205A (en) * | 2010-03-30 | 2010-07-21 | 丽水市南明化工有限公司 | Method for synthesizing substitutional crylic acid phenyl ester |
Non-Patent Citations (1)
| Title |
|---|
| 沈德渊等: "连续加料蒸馏法制备丙烯酰氯", 《南京林业大学学报(自然科学版)》, vol. 25, no. 5, 30 September 2001 (2001-09-30) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553526A (en) * | 2018-12-18 | 2019-04-02 | 杭州盛弗泰新材料科技有限公司 | A kind of continuous producing method of acryloyl chloride |
| CN115612158A (en) * | 2022-11-16 | 2023-01-17 | 山东华业包装科技股份有限公司 | Glassine-like polypropylene film |
| CN115612158B (en) * | 2022-11-16 | 2023-06-20 | 山东华业包装科技股份有限公司 | Glass paper-like polypropylene film |
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