CN102584579B - Preparation process of hydroxyethyl methacrylate - Google Patents
Preparation process of hydroxyethyl methacrylate Download PDFInfo
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- CN102584579B CN102584579B CN 201210012409 CN201210012409A CN102584579B CN 102584579 B CN102584579 B CN 102584579B CN 201210012409 CN201210012409 CN 201210012409 CN 201210012409 A CN201210012409 A CN 201210012409A CN 102584579 B CN102584579 B CN 102584579B
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Abstract
The invention relates to a preparation process of hydroxyethyl methacrylate. The preparation process comprises the following steps of: sucking methacrylic acid, a catalyst, a polymerization inhibitor and water in vacuum, keeping the vacuum degree at between -0.99Mpa and 0.75Mpa, charging nitrogen gas, ensuring that the volume ratio of oxygen to nitrogen gas is 0.01-0.25 percent, heating to 80-85 DEG C, dropwise adding epoxy ethane, ensuring that the pressure is less than or equal to 60KPa by controlling the dripping speed of epoxy ethane, and cooling with cooling water to control the reaction temperature at 90-100 DEG C, wherein the molar ratio of epoxy ethane to methacrylic acid is (1.02-1.06):1; after dropwise adding, stopping adding cooling water, naturally raising the temperature, and sampling and detecting whether the mass percentage of methacrylic acid is less than 0.5 percent after the temperature is lowered, and if so, ending an addition reaction; and after the addition reaction is completed, removing light component epoxy ethane, water and methacrylic acid in absolute vacuum, transferring an intermediate product into a middle kettle, adding 0.05-0.5 percent by mass water, and distilling under reduced pressure to obtain hydroxyethyl methacrylate. The product, i.e., hydroxyethyl methacrylate prepared with the method has high content and small impurity content.
Description
Technical field
The present invention relates to the preparation technology field of hydroxyethyl methacrylate ester, be specifically related to the preparation technology of methacrylic acid hydroxyl ethyl ester.
Background technology
Esters of acrylic acid can be divided into general acrylate and Specialty Acrylates by molecular structure and application.Wherein Specialty Acrylates output is relatively low, the industrial scale less, but its kind is a lot.In numerous Specialty Acrylates, methacrylic acid hydroxyl ethyl ester is a kind of colourless transparent liquid, there are two functional groups of carbon-carbon double bond and hydroxyl, character ripple extremely alive, range of application is quite extensive, mainly for the manufacture of the Hydroxylated acrylic resin that active group is arranged, coatings industry and epoxy resin, vulcabond etc.
The preparation method of methacrylic acid hydroxyl ethyl ester (HEMA) is a lot, at present the most frequently used on suitability for industrialized production is the ring-opening reaction method, progressively be added drop-wise in methacrylic acid reaction synthesize methyl acrylic acid hydroxy methacrylate under the acting in conjunction of catalyzer, stopper than by oxyethane by certain alkanoic acid in reactor.The preparation technology of methacrylic acid hydroxyl ethyl ester as original as our company is as follows: methacrylic acid (MAA) is pumped in reactor, then add catalyzer, stopper, in heat-conducting oil heating to 80-85 ℃, dripping oxyethane (EO) under nitrogen protection under normal pressure 80-90 ℃ condition carries out addition reaction (reaction times is relevant with charging capacity, the larger reaction times of charging capacity is longer, as worked as methacrylic acid 200kg, unclassified stores proportionally adds fashionable, reaction times 2.5-3.5 hour), closing water coolant after being added dropwise to complete heats up naturally, after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete, pump into after completion of the reaction still kettle, underpressure distillation condensation under the about 120--280 of heat-conducting oil heating ℃ condition, isolate light constituent and heavy constituent, middle runnings is this product.CN101891613 also discloses a kind of preparation method of methacrylic acid hydroxyl ethyl ester: agitator will be housed, thermometer, the flask of reflux condensing tube is placed in water-bath, add Indian red, Resorcinol and methacrylic acid, heating in water bath is to 80-85 ℃, with the air in the nitrogen replacement reaction flask, after being dissolved in methacrylic acid fully, Indian red starts to pass into oxyethane, aeration time 4 hours, after finishing, ventilation continues reaction 1 hour, then reactant is proceeded in matrass, add again appropriate Resorcinol underpressure distillation, the cut of collecting 82-85 ℃ is finished product.The technical process of different manufacturers is basic identical, at processing parameters such as selecting catalyst, stopper, temperature of reaction, times, slightly has any different.
Above-mentioned preparation technology's technical problem underlying is:
1, side reaction is more, generates the impurity such as dibasic acid esters monoesters, dibasic acid esters, and foreign matter content is difficult to control.
2, under condition of normal pressure, oxyethane is seriously excessive, easily forms explosive mixed gas, and danger is higher.
3, the easy polymerization of methacrylic acid hydroxyl ethyl ester, number of polymers is more difficult.
4,, under aerobic conditions, oxyethane easily forms the Combination explosive substance; Under oxygen free condition, polymerization easily occurs in raw material and product, is difficult to control oxygen level under normal pressure.
Thereby 5, the methacrylic acid rear easy polymerization of being heated causes implode, and discharge amount of heat.
6, the simple distillation carbon residue is more, and yield is low and produce a large amount of waste residues.
For the problems referred to above, the technician mentions only having the further purification of the rectifying tower of employing just can improve product content and reduce the impurity such as dibasic acid esters, monoesters in side reaction by exchanging between person skilled in the industry.To easy polymerization in methacrylic acid hydroxyl ethyl ester production process, adopting high vacuum to reduce service temperature controls.But adopt rectifying tower, polymerization to adopt high vacuum high to equipment requirements, will inevitably increase production cost.
Technology contents
The technical problem that at first the present invention will solve is that side reaction is more, generates the impurity such as dibasic acid esters, monoesters; Under condition of normal pressure, oxyethane is seriously excessive, easily forms explosive mixed gas, and danger is higher.The present invention adds appropriate water as auxiliary agent in reactor for this reason, and carries out in confined conditions addition reaction, and result has solved above-mentioned technical problem effectively.
Technical scheme of the present invention is as follows: by the vacuum unit, reactor is evacuated, keep the reactor vacuum state, utilize vacuum by methacrylic acid, catalyzer, stopper, water suction reactor, the mass percent of catalyzer, stopper, water and methacrylic acid is respectively 0.5 * 10
-2-2 * 10
-2, 4.5 * 10
-4-3 * 10
-4, 0.5 * 10
-3-5 * 10
-3, after completing in the assurance reactor vacuum-0.99Mpa--0.75Mpa, be filled with nitrogen and guarantee oxygen/nitrogen volume ratio 0.01%-0.25%, be heated to drip oxyethane under 80 ℃ of-85 ℃ of conditions, the speed of dripping by the gate ring oxidative ethane guarantees reacting kettle inner pressure≤60KPa, oxyethane and methacrylic acid mol ratio are 1.02-1.06:1, (reaction times is relevant with charging capacity at 90-100 ℃ to control temperature of reaction by water quench, the larger reaction times of charging capacity is longer, as worked as methacrylic acid 2000kg, unclassified stores proportionally adds fashionable, reaction times 1.5-3.5 hour), close water coolant after being added dropwise to complete and naturally heat up, after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete, after addition reaction, decompression removes light constituent oxyethane, water and methacrylic acid, and in the middle of middle product are gone to, underpressure distillation after the water of still interpolation mass percent 0.5-5 ‰, obtain methacrylic acid hydroxyl ethyl ester.
Described catalyzer is not particularly limited, can be selected from one or more in the iron cpds such as the chromium cpds such as methacrylic acid chromium, chromium chloride, chromium acetylacetonate, chromium acetate, methyl sodium dichromate 99, methacrylic acid chromium, iron(ic) chloride, iron powder, ironic formiate, methacrylic acid iron, preferably chromium acetate.
Described stopper is not particularly limited, can be selected from one or more in amine compound, hydroquinone monomethyl ether, the MEHQ such as the phenolic compounds such as Resorcinol, methyl hydroquinone, Tert. Butyl Hydroquinone, Vermitin, phenothiazine, preferably Resorcinol, MEHQ.
The invention technician makes improvements existing method through test for many years, and the aforesaid method difference with the prior art mainly contains 3 points: 1, under air tight condition, carry out addition reaction; 2, add water as auxiliary agent; 3, temperature of reaction is controlled at 90-100 ℃.
The technique effect that air tight condition carries out addition reaction is the leakage that prevents oxyethane, reduce more environmental protection of pollution to environment, reduced the consumption of oxyethane, reduce raw materials cost, avoid the explosive mixed gas of the excessive formation of oxyethane, increase the security of producing, stability.
In order to reach international quality standard, the invention technician thinks and has increased the content that a set of rectifying tower system just effectively raises product purity to the product rectification and purification and reduces dibasic acid esters and monoesters in side reaction newly by exchanging between person skilled in the industry, because the restriction technologies personnel of equipment self want to solve the problems referred to above from the adjustment of self technique, find that by long-term lot of experiments shorter dibasic acid esters content of this product reaction times is lower, lot of experimental data finds that the consumption of catalyzer is larger, and the reaction times is shorter; Temperature of reaction is higher, and the reaction times is shorter.But the raising of catalyst levels has increased production cost virtually, also environment has been caused to detrimentally affect, and temperature more the high-risk coefficient is larger.Considering the technician finds most economical effective means to solve the higher technical problem of above-mentioned foreign matter content finally---and add water as auxiliary agent, the technique effect that adds water generates is that product dibasic acid esters, monoester content descend and effectively reduced the generation of polymkeric substance in the production process.The analysis reason is as follows: the impurity dibasic acid esters in product is by methacrylic acid hydroxyl ethyl ester (HEMA) and further esterification generation of methacrylic acid (MAA), this esterification also generates water simultaneously, add after auxiliary agent water and make this esterification to being unfavorable for that the reversed reaction direction that generates dibasic acid esters carries out, so dibasic acid esters content descends; Monoesters in product is formed by HEMA and EO reaction response, add after auxiliary agent water because the H on the unstable HEMA of the capturing hydroxyl of oxyethane (EO) generates, adding of water may make unsettled EO more easily capture the H on the water hydroxyl, thereby reduces the generation of monoesters; Monoesters reduces also and may reduce relevant with EO add-on under air tight condition; Methacrylic acid hydroxyl ethyl ester contains two keys, easy polymerization reaction take place, vaporizer distillation 4-8 pot just produces more polymkeric substance, carry out again underpressure distillation after adding auxiliary agent water, can produce continuously only a small amount of polymkeric substance of 60-100 pot, the analysis reason is as follows: polymkeric substance is also mainly to open polymerization and form due to the continuous esterification of unsettled hydroxyl in HEMA and two keys, and the esterification in this process also can generate water, has stoped this type of esterification after adding auxiliary agent water; The reaction energy that the part side reaction needs has been taken away in the volatilization of water.Secondly find polymkeric substance is soaked in hot water and can melt fully in certain hour through lot of experiments, may dissolve the polymkeric substance in the part producing process after adding certain proportion water.
The temperature of reaction of the standby methacrylic acid hydroxyl ethyl ester of ring-opening reaction legal system commonly used is 50-90 ℃, and temperature of reaction of the present invention is controlled at 90-100 ℃, and speed of reaction is very fast, and the reaction times is short, and production efficiency is high.After the speed of reaction height, the corresponding minimizing of the catalyst levels of relative usage, thus reduce the impurity in product, not only effectively reduce production cost, more reduced the harm to environment.Next reaction times is shorter, and side reaction is fewer, has also reduced to a certain extent dibasic acid esters content.
Another improvement of the present invention is after addition reaction, remove light constituent oxyethane, water and methacrylic acid before, cooling water temperature is to 30-70 ℃, subsequently the water coolant in the venting chuck.Remove oxyethane and methacrylic acid and be for fear of EO, MAA in still-process and HEMA polymerization occurs, do not produce the 2-4 pot in de-light process before improving, reactor has just formed number of polymers, adopt the low temperature drainage technology can effectively reduce this Type of Collective in reactor, de-light process is produced the 40-80 pot continuously, and reactor is not found polymkeric substance.The reason that the technician analyzes may be as follows: temperature reduces can suppress polyreaction; Now as not in time discharge the water of lesser temps, gas phase is partly met the easy condensation of cold water, thereby be adsorbed on the reactor wall, because gas phase part level of inhibitor is lower, very easily polymerization under hot conditions, thus the water coolant now in the venting chuck is avoided the gas phase part, in the condensation of still wall, polymerization occurs even causing further implode.So cooling draining has simultaneously herein just greatly reduced polymerization.
As preferably, being heated to 80 ℃--85 ℃ of described heating refer to steam heating.Vapor temperature only only has 80-120 ℃, avoids the thermal oil excess Temperature easily to cause and catch fire, next the inhomogeneous local heating of thermal oil initiated polymerization, the danger of generation implode.
As preferably, in the middle of middle product go to, the distillation of still adopts thin film evaporation, and vacuum degree control, at 5.33-21.33Kpa, is controlled vapor pressure 10-50Kpa, still second distillation in the middle of raffinate returns.In thin film evaporation, feed liquid is membranaceous flowing and is conducted heat and evaporate along the heating tube wall, and advantage is that heat transfer efficiency is high, and velocity of evaporation is fast, and residence time of material is short, is particularly suitable for the evaporation of heat-sensitive substance.The present invention uses thin film evaporation there is no the coking residue, makes more environmental protection of whole technique, safer.
As preferably, remove light constituent oxyethane, water and methacrylic acid under be decompressed to after addition reaction-1.0mpa.
The inventive method prepares HEMA after for some time, still can lingering section puffed rice shaped polymer in reactor, distiller, and this polymkeric substance is well known to a person skilled in the art, but there is no at present its composition of bibliographical information and form reason.Fast these polymkeric substance of cleaning are to guarantee the quantity-produced prerequisite, but do not find before reasonable treatment process, usually with electric drill, beat or hammer strikes, and extremely waste time and energy, and residual product or raw material are easily burnt and cleaned workman's eyes.Be to provide the method for periodic cleaning polymkeric substance as another improvements of the present invention: high temperature poach under alkaline condition.The technician finds that other laboratories solvent commonly used all can't effectively dissolve as ethanol, N-BUTYL ACETATE, dimethylbenzene etc. through great many of experiments, and alkaline condition high temperature poach reduces time of a large amount of labor cleaning's polymkeric substance, more environmental protection, safer, more efficient.
In sum, technique effect of the present invention is: products obtained therefrom methacrylic acid hydroxyl ethyl ester content is high, foreign matter content is few; The oxyethane consumption reduces, and avoids forming explosive mixed gas; Production technique is safer, environmental protection.
The accompanying drawing explanation
Fig. 1 embodiment 1 method gained methacrylic acid hydroxyl ethyl ester product gas chromatogram
Fig. 2 embodiment 2 method gained methacrylic acid hydroxyl ethyl ester product gas chromatograms
Fig. 3 embodiment 3 method gained methacrylic acid hydroxyl ethyl ester product gas chromatograms
Fig. 4 embodiment 4 method gained methacrylic acid hydroxyl ethyl ester product gas chromatograms
Embodiment
The embodiment 1 original preparation technology of our company
The 200kg methacrylic acid is pumped in reactor, then by proportioning, add the chromium acetate, 4.5 * 10 that massfraction is 0.5%
-4resorcinol and MEHQ; in heat-conducting oil heating to 80-85 ℃; drip oxyethane under nitrogen protection under normal pressure 80-100 ℃ condition and carry out addition reaction approximately 3 hours; oxyethane and methacrylic acid mol ratio are to close water coolant after 1.08:1 is added dropwise to complete naturally to heat up; after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete; pump into after completion of the reaction still kettle; underpressure distillation condensation under the about 120--280 of heat-conducting oil heating ℃ condition; isolate light constituent and heavy constituent, middle runnings is this product.
Adopt the gc analysis product composition, GC conditions: capillary chromatographic column (SE-54), 170 ℃ of column temperatures, 230 ℃ of injector temperatures, the vaporizer temperature: 230 ℃, flame ionization ditector (FID) temperature: 230 ℃, sample size: 0.2 μ l, carrier gas N
2, nebulizer gas pressure 0.06Mpa, splitting ratio 1:30.
The gained color atlas is shown in accompanying drawing 1, and adopt the area normalization method analytical results in Table 1: what wherein retention time was 2.668min is the chromatographic peak of principal constituent methacrylic acid hydroxyl ethyl ester, and content is 95.77%; 4.483min be the dibasic acid esters peak, content is 0.8135%; 4.228min be the monoesters peak, content is 3.0675%.
Table 1
By vacuum suction methacrylic acid 2000kg, the chromium acetate that massfraction is 0.5%, 4.5 * 10
-4resorcinol and MEHQ, after completing, the assurance vacuum is at-0.99Mpa---0.75Mpa, be filled with nitrogen and guarantee oxygen/nitrogen volume ratio 0.01%, be heated to 80 ℃--drip oxyethane under 85 ℃ of conditions, the speed of dripping by the gate ring oxidative ethane guarantees pressure≤60KPa, oxyethane and methacrylic acid mol ratio are 1.06:1, by water quench, control temperature of reaction at 100 ℃, react 3.5 hours; Close water coolant after being added dropwise to complete and naturally heat up, after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete; Remove light constituent oxyethane, water and methacrylic acid after addition reaction under perfect vacuum, the water that in the middle of middle product are gone to, still adds mass percent 5 ‰, by the thin-film evaporator continuous still battery, obtains methacrylic acid hydroxyl ethyl ester.
Adopt the gc analysis product composition, GC conditions is with embodiment 1.The gained color atlas is shown in accompanying drawing 2, and adopt the area normalization method analytical results in Table 2: what wherein retention time was 2.757min is the chromatographic peak of principal constituent methacrylic acid hydroxyl ethyl ester, and content is 95.99%; 4.573min be the dibasic acid esters peak, content is 0.30%; 4.323min be the monoesters peak, content is 3.04%.With original method of embodiment 1, compare, methacrylic acid hydroxyl ethyl ester content raises, and impurity monoesters, dibasic acid esters content descend.
Table 2
By vacuum suction methacrylic acid 2000kg, the chromium acetate that massfraction is 0.5%, 4.5 * 10
-4resorcinol and MEHQ and 0.5 * 10
-3water, after completing the assurance vacuum-0.99Mpa--0.75Mpa, be filled with nitrogen and guarantee oxygen/nitrogen volume ratio 0.01%, be heated to drip oxyethane under 80 ℃ of-85 ℃ of conditions, the speed of dripping by the gate ring oxidative ethane guarantees pressure≤60KPa, oxyethane and methacrylic acid mol ratio are 1.06:1, by water quench, control temperature of reaction at 90 ℃, react 3.5 hours; Close water coolant after being added dropwise to complete and naturally heat up, after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete; Remove light constituent oxyethane, water and methacrylic acid after addition reaction under perfect vacuum, the water that in the middle of middle product are gone to, still adds mass percent 5 ‰, by the thin-film evaporator continuous still battery, obtains methacrylic acid hydroxyl ethyl ester.
Adopt the gc analysis product composition, GC conditions is with embodiment 1.The gained color atlas is shown in accompanying drawing 3, and adopt the area normalization method analytical results in Table 3: what wherein retention time was 2.648min is the chromatographic peak of principal constituent methacrylic acid hydroxyl ethyl ester, and content is 97.64%; 4.392min be the dibasic acid esters peak, content is 0.22%; 4.135min be the monoesters peak, content is 1.77%.With original method of embodiment 1, compare, methacrylic acid hydroxyl ethyl ester content significantly raises, and impurity monoesters, dibasic acid esters content significantly descend.With embodiment 2, than methacrylic acid hydroxyl ethyl ester content, raise, impurity monoesters, dibasic acid esters content descend.
Table 3
The preparation method that embodiment 4 the present invention add auxiliary agent water, cooling water temperature and get rid of
By vacuum suction methacrylic acid 2000kg, the chromium acetate that massfraction is 2.0%, 13 * 10
-4resorcinol and MEHQ and 5 * 10
-3water, after completing, the assurance vacuum is at-0.99Mpa---0.75Mpa, be filled with nitrogen and guarantee oxygen/nitrogen volume ratio 0.25%, be steam heated to 80 ℃--drip oxyethane under 85 ℃ of conditions, the speed of dripping by the gate ring oxidative ethane guarantees pressure≤60KPa, oxyethane and methacrylic acid mol ratio are 1.02:1, by water quench, control temperature of reaction at 100 ℃, 1.5 hours reaction times; Close water coolant after being added dropwise to complete and naturally heat up, after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete; After addition reaction, cooling water temperature is to 30-70 ℃, water coolant in the venting chuck subsequently, remove light constituent oxyethane, water and methacrylic acid under perfect vacuum, still in the middle of middle product are gone to, add the water of mass percent 0.5 ‰, adopt thin film evaporation, vacuum degree control, at 5.33-21.33Kpa, is controlled vapor pressure 10-50Kpa, and in the middle of raffinate returns, the still second distillation obtains methacrylic acid hydroxyl ethyl ester.
Adopt the gc analysis product composition, GC conditions is with embodiment 1.The gained color atlas is shown in accompanying drawing 4, and adopt the area normalization method analytical results in Table 4: what wherein retention time was 2.728min is the chromatographic peak of principal constituent methacrylic acid hydroxyl ethyl ester, and content is 98.63%; 4.568min be the dibasic acid esters peak, content is 0.12%; 4.283min be the monoesters peak, content is 0.83%.With original method of embodiment 1, compare, methacrylic acid hydroxyl ethyl ester content significantly raises, and impurity monoesters, dibasic acid esters content significantly descend.With embodiment 2,3, than methacrylic acid hydroxyl ethyl ester content, raise, impurity monoesters, dibasic acid esters content descend.
Table 4
Other indexs of embodiment 5 products
Detect embodiment 1,2,3 product free acids (in methacrylic acid), moisture, colourity, level of inhibitor, method is respectively according to acid base titration, GB/T6283, GB/T605-2006, GB/T17530.5.The results are shown in Table 5:
Table 5
Contrast table 5 data are visible, and this technological operation is simple, efficient.Quality product has reached the advanced technologies product quality level, meets international quality common index.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, the relevant staff can, in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to the claim scope.
Claims (8)
1. the preparation technology of a methacrylic acid hydroxyl ethyl ester, it is characterized in that: by the vacuum unit, reactor is evacuated, keep the reactor vacuum state, utilize vacuum by methacrylic acid, catalyzer, stopper, water suction reactor, the mass ratio of catalyzer, stopper, water and methacrylic acid is respectively 0.5 * 10
-2-2 * 10
-2, 4.5 * 10
-4-13 * 10
-4, 0.5 * 10
-3-5 * 10
-3after completing in the assurance reactor vacuum-0.99Mpa--0.75Mpa, be filled with nitrogen and guarantee oxygen/nitrogen volume ratio 0.01%-0.25%, be heated to drip oxyethane under 80 ℃ of-85 ℃ of conditions, the speed of dripping by the gate ring oxidative ethane guarantees reacting kettle inner pressure≤60KPa, oxyethane and methacrylic acid mol ratio are 1.02-1.06:1, by water quench, control temperature of reaction at 90-100 ℃; Close water coolant after being added dropwise to complete and naturally heat up, after temperature descends, sampling detects the methacrylic acid mass percent and is less than 0.5% to be considered as addition reaction complete; After addition reaction, decompression removes light constituent oxyethane, water and methacrylic acid, and in the middle of middle product are gone to, underpressure distillation after the water of still interpolation mass percent 0.5-5 ‰, obtain methacrylic acid hydroxyl ethyl ester.
2. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1, it is characterized in that: described catalyzer is selected from one or more in methacrylic acid chromium, chromium chloride, chromium acetylacetonate, chromium acetate, iron(ic) chloride, iron powder, ironic formiate, methacrylic acid iron.
3. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1, it is characterized in that: described stopper is selected from one or more in Resorcinol, methyl hydroquinone, Tert. Butyl Hydroquinone, Vermitin, thiodiphenylamine, hydroquinone monomethyl ether, MEHQ.
4. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1 is characterized in that: after addition reaction, remove light constituent oxyethane, water and methacrylic acid before, cooling water temperature is to 30-70 ℃, subsequently the water coolant in the venting chuck.
5. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1, is characterized in that: be heated to 80 ℃ of-85 ℃ of described heating and refer to steam heating.
6. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1, it is characterized in that: in the middle of middle product go to, the distillation of still adopts thin film evaporation, vacuum degree control, at 5.33-21.33Kpa, is controlled vapor pressure 10-50Kpa, still second distillation in the middle of raffinate returns.
7. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1, it is characterized in that: be decompressed to after addition reaction-1.0Mpa removes light constituent oxyethane, water and methacrylic acid.
8. the preparation technology of methacrylic acid hydroxyl ethyl ester claimed in claim 1, is characterized in that: prepare methacrylic acid hydroxyl ethyl ester after for some time, the polymkeric substance produced in high temperature poach production process under alkaline condition.
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| US20170183288A1 (en) * | 2014-07-14 | 2017-06-29 | Wanhua Chemical Group Co., Ltd. | Method for preparing hydroxyethyl (meth) acrylate |
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| CN109053450A (en) * | 2018-07-03 | 2018-12-21 | 青岛科技大学 | A kind of preparation method for the 4- hy-droxybutyl being separated by extraction |
| CN110922330B (en) * | 2019-11-22 | 2022-08-26 | 广东新华粤石化集团股份公司 | Preparation method of hydroxyethyl acrylate |
| CN111234796A (en) * | 2020-01-21 | 2020-06-05 | 中国石油天然气股份有限公司 | Surfactant and preparation method thereof |
| CN114181084B (en) * | 2021-12-13 | 2023-11-14 | 山东省海洋化工科学研究院 | Purification method of acetoacetyl ethyl methacrylate |
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| US20170183288A1 (en) * | 2014-07-14 | 2017-06-29 | Wanhua Chemical Group Co., Ltd. | Method for preparing hydroxyethyl (meth) acrylate |
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