CN1537095A - Method of production for (meth) acrylic ester - Google Patents
Method of production for (meth) acrylic ester Download PDFInfo
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- CN1537095A CN1537095A CNA038007495A CN03800749A CN1537095A CN 1537095 A CN1537095 A CN 1537095A CN A038007495 A CNA038007495 A CN A038007495A CN 03800749 A CN03800749 A CN 03800749A CN 1537095 A CN1537095 A CN 1537095A
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- methyl
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- acrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing a (meth)acrylic ester which comprises feeding (meth)acrylic acid and an alcohol to a reactor, wherein a polymerization inhibitor is dissolved in the reaction mixture and the reaction is conducted while keeping the reaction mixture containing the polymerization inhibitor dissolved therein in contact with a member present in the gas-phase part of the reactor. Thus, the (meth)acrylic acid and the acrylic ester are prevented from polymerizing on the member present in the gas-phase part of the reactor, and a continuous operation can be conducted over long.
Description
Technical field
The present invention relates to the preparation method of (methyl) acrylate, (methyl) vinylformic acid means one or both in vinylformic acid and the methacrylic acid.
Background technology
As everyone knows, (methyl) acrylate is the high liquid of polymerizability, in order to prevent its polymerization, knownly makes it contain polymerizations such as quinhydrones, thiodiphenylamine to prevent agent (for example, the spy opens the 2000-355570 communique).
Yet, when supplying with (methyl) vinylformic acid and alcohol toward reactor and prepare (methyl) acrylate, make polymerization prevent that agent is dissolved in the reaction solution, in the parts of the top board reactor gas phase portions such as (manhole (マ Application ホ one Le)) of reactor, because the vapor generation condensation of (methyl) vinylformic acid and (methyl) acrylate, in this phlegma, carrying out polymerization, so, can not move continuously for a long time.
The present invention is in view of above-mentioned practical situation, purpose provides (methyl) vinylformic acid in a kind of parts that prevent to be present in reactor gas phase portion and the polymerization of (methyl) acrylate, (methyl) acrylate preparation method that can move continuously for a long time, improvement.
Description of drawings
Fig. 1 is the cross sectional illustration figure of one of the preferred reactor that uses and attendant equipment thereof example among the present invention.
Summary of the invention
Main points of the present invention provide the preparation method of a kind of (methyl) acrylate, it is characterized in that, when past reactor supply (methyl) vinylformic acid and alcohol prepare (methyl) acrylate, make the polymerization prevent that agent is dissolved in the reaction solution, dissolved reaction solution that polymerization prevents agent and contact with the parts that are present in reactor gas phase portion on one side and react Yi Bian make.
Explain the present invention according to accompanying drawing below.
Basically with in the past known method is identical in the preparation of the present invention's (methyl) acrylate.
Acrylate by the present invention's preparation can be enumerated methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-EHA, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid methoxyl group ethyl ester etc.Methacrylic ester by the present invention's preparation can be enumerated the various methacrylic esters corresponding with the aforesaid propylene acid esters, for example, and methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate etc.
In the present invention, as raw alcohol, can use and the corresponding various alcohol of above-mentioned (methyl) acrylate.The reaction of (methyl) vinylformic acid and alcohol is carried out in the presence of an acidic catalyst usually, can use tosic acid etc. as an acidic catalyst.
Industrial, above-mentioned reaction can be carried out continuously.That is,, (methyl) acrylate and the water byproduct that generate are extracted out from reactor continuously (methyl) vinylformic acid and the continuous supply response device of alcohol.Alcohol is generally 0.5～2 to (methyl) acrylic acid supply mol ratio, and temperature of reaction is generally 80～100 ℃, and reaction pressure is generally 25～70kPa, and the reaction times (residence time) is generally 1～5 hour.
Prevent agent as polymerization, can use various phenolic compound, phenothiazine compounds, copper compound etc.As phenolic compound, can enumerate quinhydrones, methoxyl group quinhydrones, pyrogallol, catechol, Resorcinol etc., as phenothiazine compounds, can enumerate thiodiphenylamine, two-(α-Jia Jibianji) thiodiphenylamine, two-(α-Er Jiajibianji) thiodiphenylamine, 3,7-dioctyl thiodiphenylamine etc., as copper compound, can enumerate cupric chloride, neutralized verdigris, copper carbonate, vinylformic acid copper, cupric dimethyldithiocarbamate etc.
Polymerization prevents to use after agent is dissolved in appropriate solvent, as this solvent, for example, when being phenolic compound, can enumerate water, acetic acid, (methyl) vinylformic acid, (methyl) acrylate, aromatics, ketone compound, alcohol etc.Polymerization in the reaction solution prevents that agent concentration is generally 0.01～1.5 weight %.
In the present invention, preferably use stirring tank reactor shown in Figure 1.The structure that stirs tank reactor is, slightly is on the hemispheric cylinder 1 in two sides 11 agitator 2 is set.The pre-portion of cylinder 1 has the manhole 4 that is used to extract the vapour pipe 3 of water byproduct out and detects usefulness.In addition, in the inside of cylinder 1,, be divided into the seed cell of suitable capacity with dividing plate 5 according to reacting the required residence time.At this moment, the connecting tube 61 of the band valve (not shown) of each seed cell by being arranged on cylinder 1 outside is connected, and in each seed cell agitator 2 is set.
Raw material (methyl) vinylformic acid and alcohol are supplied with from the top of reactor one end by pump (not shown), and product (methyl) acrylate is extracted out from the bottom of the reactor the other end by pump 7.And water byproduct is extracted out from vapour pipe 3.
Feature of the present invention is, prevents that the reaction solution of agent from contacting with the parts that are present in reactor gas phase portion on one side and reacts Yi Bian dissolved polymerization.That is, in the present invention, by with containing the wetting parts that are present in reactor gas phase portion of reaction solution that polymerization prevents agent, prevent the polymerization of (methyl) acrylate etc. at the position that is stored in reactor gas phase portion.
As the parts that are present in reactor gas phase portion, under the situation of example shown in Figure 1, can enumerate the top board of manhole 4, cylinder 1 etc.Contact method to above-mentioned reaction solution and parts is not particularly limited, but is preferred with pump from the method for nozzle spray reaction solution.For example, the discharge side pipe road 62 (reaction solution is extracted out and used pipeline) that extracts the pump 7 that above-mentioned reaction solution uses links to each other with reaction solution service 63 arms, in the end of this reaction solution service nozzle 8 is set.In this case,, expose the gas phase portion of reactor as long as reaction solution service 63 is configured in from the position, space on bottom to the top of cylinder 1, because the pipe section that causes (methyl) acrylic ester polymerization is reduced, so be preferred.The kenel of nozzle 8 can suitably be selected, and for example, when 4 sprayings of the narrow and small manhole of area, adopts conical nozzle, and when the top board spraying of broad dividing plate 5 of area or cylinder 1, it is preferred adopting wide-angle fan type nozzle.
In the present invention, in order to remove the solids of accumulating in the reaction solution continuously, it is preferred that filter screen (ス ト レ one Na one) (9) is set at the middle part of reaction solution service (63).In example shown in Figure 1,2 filter screens (9) that can be used alternatingly are set.The sieve mesh of filter screen (9) usually more than 30 orders, preferred 60～100 orders.In addition, under meter (6f) and pressure warning unit (6p) are set at the middle part of reaction solution service (63), the reaction solution flow of controlling supplying-nozzle (8) whereby is preferred.The feed rate of reaction solution, if often in addition wetting the parts of reactor gas phase portion existence with reaction solution, and be not particularly limited, but usually more than 200L/Hr, preferably at 200～800L/Hr.
Optimum implementation of the present invention
Below, be described more specifically the present invention by embodiment, but main points of the present invention are not limited to these, are not subjected to the restriction of the following example.
Use the stainless steel (SUS316L) same to stir tank reactor with being shown in Fig. 1.The diameter of cylinder (1) is that 3000mm, length are 6000mm.The diameter of manhole 4 is that the height of 500mm, dividing plate 5 is 2800mm.
Supply with vinylformic acid and butanols toward above-mentioned steel basin type reactor, resupply tosic acid and make its concentration in reaction solution reach the quinhydrones of 1 weight % and 0.03 weight %, quinhydrones is supplied with the butanol solution of 8 weight % concentration.Then, under 94 ℃ of temperature of reaction, reaction pressure 35kPa, the condition in 3 hours reaction times (residence time), carry out esterification continuously.
During esterification, respectively facing to all surfaces of the space exposed portions serve of the top board of manhole 4, cylinder 1, dividing plate 5, from nozzle 8 spray reaction liquid.Spray amount is 330L/Hr to manhole 4, is 580L/Hr to the top board of cylinder 1, is 420L/Hr to the space exposed portions serve of dividing plate 5.After moving about 1 year continuously, stopped reaction, from the parts that manhole 4 observing response device gas phase portions exist, the result does not find the adhesion of polymkeric substance.
Comparative example 1
Except not from nozzle 8 spray reaction liquid, carry out esterification similarly to Example 1 continuously.Reaction beginning back is at the solids of observing through 1 month time point on the filter screen 9, and after about 2 months, filter screen 9 is frequently stopped up by solids, and reaction stops.From the parts that manhole 4 observing response device gas phase portions exist, the result is that the top board of manhole 4, cylinder 1, the space exposed portions serve of dividing plate 5 are found the adhesion of polymkeric substance, and peeling off the result who surveys its gross weight in the back is 200kg.
Adaptability on the industry
The preparation method of (methyl) acrylate of the invention described above can prevent that reactor gas phase section from existing Parts in the polymerization of (methyl) acrylate etc., can long-time continuous carry out polymerization.
Claims (2)
1. the preparation method of (methyl) acrylate, it is characterized in that, when supplying with (methyl) vinylformic acid and alcohol preparation (methyl) acrylate toward reactor, polymerization is prevented that agent is dissolved in the reaction solution, dissolved reaction solution that polymerization prevents agent and contact with the parts that are present in reactor gas phase portion on one side and react Yi Bian make.
2. preparation method according to claim 1 wherein, is provided with nozzle on the top of reaction solution service, from this nozzle to the parts spray reaction liquid that is present in reactor gas phase portion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002021374 | 2002-01-30 | ||
| JP21374/2002 | 2002-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1537095A true CN1537095A (en) | 2004-10-13 |
Family
ID=27654389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA038007495A Pending CN1537095A (en) | 2002-01-30 | 2003-01-23 | Method of production for (meth) acrylic ester |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1537095A (en) |
| WO (1) | WO2003064370A1 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3843843A1 (en) * | 1988-12-24 | 1990-07-05 | Henkel Kgaa | METHOD FOR IMPROVED PRODUCTION OF (METH) ACRYLIC ACIDES OF PRESCRIBED ALCOHOLS (IV) |
| JP3787261B2 (en) * | 1999-04-16 | 2006-06-21 | 株式会社日本触媒 | Method for preventing polymerization of easily polymerizable compounds |
-
2003
- 2003-01-23 CN CNA038007495A patent/CN1537095A/en active Pending
- 2003-01-23 WO PCT/JP2003/000594 patent/WO2003064370A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| WO2003064370A1 (en) | 2003-08-07 |
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